High flow, high heat polycarbonate compositions

ABSTRACT

Polycarbonate blend compositions are disclosed. The compositions include at least one polycarbonate useful for high heat applications. The compositions include at least one poly(aliphatic ester)-polycarbonate. The compositions can include one or more additional polymers. The compositions can include one or more additives. The compositions can be used to prepare articles of manufacture.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/025,926, filed Jul. 17, 2014, which is herein incorporated byreference in its entirety.

TECHNICAL FIELD

The present disclosure relates generally to polycarbonate compositions,methods of using the compositions, and processes for preparing thecompositions. In particular, the disclosure relates to polycarbonatecompositions having improved thermal, mechanical, rheological or flameretardant properties. The disclosure also relates to articles comprisingthe polycarbonate compositions.

BACKGROUND

Polycarbonates (PC) are synthetic thermoplastic resins that can bederived from bisphenols and phosgenes by interfacial polymerization, orfrom bisphenols and diaryl carbonates by melt polymerization.Polycarbonates are a useful class of polymers having many desiredproperties. They are highly regarded for optical clarity and enhancedimpact strength and ductility at room temperature.

Since part designs are becoming more and more complex, a need remainsfor materials that have an improved balance of properties (e.g., heatresistance, melt flow, impact resistance, and metallizability). Inparticular, there remains a need for improved polycarbonatecompositions, and articles formed from such compositions.

SUMMARY

In one aspect, disclosed is an article including a thermoplasticcomposition comprising: (a) a first polycarbonate; (b) a poly(aliphaticester)-polycarbonate copolymer; and (c) optionally a secondpolycarbonate; wherein the composition has a heat deflection temperatureof at least 120° C., measured at 1.8 megapascals (Mpa) in accordancewith ASTM D 648; wherein the composition has a melt viscosity of lessthan 130 Pascals-seconds (Pa·s), measured in accordance with ISO 11443at 316° C. at a shear rate of 5000 reciprocal seconds (s⁻¹).

The first polycarbonate includes structural units derived from at leastone of:

wherein R^(a) and R^(b) at each occurrence are each independentlyhalogen, C₁-C₁₂ alkyl, C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂ alkoxy;p and q at each occurrence are each independently 0 to 4; R¹³ at eachoccurrence is independently a halogen or a C₁-C₆ alkyl group; c at eachoccurrence is independently 0 to 4; R¹⁴ at each occurrence isindependently a C₁-C₆ alkyl, phenyl, or phenyl substituted with up tofive halogens or C₁-C₆ alkyl groups; R^(g) at each occurrence isindependently C₁-C₁₂ alkyl or halogen, or two R^(g) groups together withthe carbon atoms to which they are attached form a four-, five, orsix-membered cycloalkyl group; and t is 0 to 10.

The poly(aliphatic ester)-polycarbonate copolymer can have the formula:

wherein m is 4 to 18; x+y is 100; and R³ is formula (I) or formula (II):

wherein R^(h) is halogen, alkyl, or haloalkyl; n is 0 to 4; and X^(a) isformula (III) or formula (IV):

wherein R^(c) and R^(d) are each independently hydrogen, halogen, alkyl,cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and R^(e) is adivalent alkyl group.

The second polycarbonate can be a Bisphenol A (BPA) polycarbonate havinga weight average molecular weight of 17,000 to 40,000 grams per mole(g/mol), as determined by gel permeation chromatography (GPC) using BPApolycarbonate standards.

The compositions, methods, and processes are further described herein.

DETAILED DESCRIPTION

The present disclosure relates to polycarbonate-based blendcompositions, also referred to herein as thermoplastic compositions. Thecompositions include at least one high heat polycarbonate and at leastone poly(aliphatic ester)-polycarbonate copolymer. The compositions caninclude one or more additional polymers (e.g., homopolycarbonates,polysiloxane-polycarbonate copolymers, polyesters). The compositions caninclude one or more additives (e.g., fillers, mold release agents,antioxidants, flame retardants). The compositions can have improvedthermal properties, mechanical properties, or rheological properties.

The compositions can comprise the combination of organophosphorus flameretardant, filler and anti-dripping agent (TSAN). This combination canbe particularly useful in obtaining an article with surprisinglyexcellent flame retardant properties, while maintaining thermal,mechanical, and rheological properties.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a.” “an” and “the” include plural references unless the context clearlydictates otherwise. The present disclosure also contemplates otherembodiments “comprising,” “consisting of” and “consisting essentiallyof,” the embodiments or elements presented herein, whether explicitlyset forth or not.

The conjunctive term “or” includes any and all combinations of one ormore listed elements associated by the conjunctive term. For example,the phrase “an apparatus comprising A or B” can refer to an apparatusincluding A where B is not present, an apparatus including B where A isnot present, or an apparatus where both A and B are present. The phrases“at least one of A, B, . . . and N” or “at least one of A, B . . . . N,or combinations thereof” are defined in the broadest sense to mean oneor more elements selected from the group comprising A, B, . . . and N,that is to say, any combination of one or more of the elements A, B, . .. or N including any one element alone or in combination with one ormore of the other elements which can also include, in combination,additional like elements not listed.

The terms “first,” “second,” “third,” and the like, as used herein, donot denote any order, quantity, or importance, but rather are used todistinguish one element from another.

“Alkyl” as used herein can mean a linear, branched, or cyclichydrocarbyl group, such as a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, isobutyl group, tert-butyl group,n-pentyl group, isopentyl group, n-hexyl group, isohexyl group,cyclopentyl group, cyclohexyl group, and the like.

“Aryl” as used herein can mean a substituted or unsubstituted arylradical containing from 6 to 36 ring carbon atoms. Examples of arylinclude, but are not limited to, a phenyl group, a bicyclic hydrocarbonfused ring system, or a tricyclic hydrocarbon fused ring system whereinone or more of the rings are a phenyl group.

“Arylalkyl” as used herein can mean an aryl, as defined herein, appendedto the parent molecular moiety through an alkyl, as defined herein.

“Copolymer” as used herein can mean a polymer derived from two or moremonomeric species, as opposed to a homopolymer, which is derived fromonly one monomer.

“Glass Transition Temperature” or “Tg” as used herein can mean themaximum temperature that a polymer, such as a polycarbonate, will haveone or more useful properties. These properties include impactresistance, stiffness, strength, and shape retention. The Tg of apolycarbonate therefore can be an indicator of its useful uppertemperature limit, particularly in plastics applications.

The Tg of a polymer, such as a polycarbonate, can depend primarily onthe composition of the polymer. Polycarbonates that are formed frommonomers having more rigid and less flexible chemical structures thanBisphenol A (BPA) generally have higher Tgs than BPA polycarbonate,while polycarbonates that are formed from monomers having less rigid andmore flexible chemical structures than BPA generally have lower Tgs thanBPA polycarbonate. For example, a polycarbonate formed from 33 mole % ofa rigid monomer, 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one(“PPPBP”), and 67 mole % BPA has a Tg of 198° C., while a polycarbonateformed from Bisphenol-A, but also having 6 wt % of siloxane units, aflexible monomer, has a Tg of 145° C. Mixing of two or morepolycarbonates having different Tgs can result in a Tg value for themixture that is intermediate between the Tgs of the polycarbonates thatare mixed. The Tg of a polycarbonate can also be an indicator of themolding or extrusion temperatures required to form polycarbonate parts.The higher the Tg of the polycarbonate the higher the molding orextrusion temperatures that are needed to form polycarbonate parts.

The Tgs described herein are measures of heat resistance of, forexample, polycarbonate and polycarbonate blends. The Tg can bedetermined by differential scanning calorimetry (DSC). The calorimetrymethod can use a TA Instruments Q1000 instrument, for example, withsetting of 20° C./min ramp rate and 40° C. start temperature and 200° C.end temperature.

“Heteroaryl” as used herein can mean any aromatic heterocyclic ringwhich can comprise an optionally benzocondensed 5 or 6 memberedheterocycle with from 1 to 3 heteroatoms selected among N, O or S. Nonlimiting examples of heteroaryl groups can include pyridyl, pyrazinyl,pyrimidinyl, pyridazinyl, indolyl, imidazolyl, thiazolyl, isothiazolyl,pyrrolyl, phenyl-pyrrolyl, furyl, phenyl-furyl, oxazolyl, isoxazotyl,pyrazolyl, thienyl, benzothienyl, isoindolinyl, benzoimidazolyl,quinolinyl, isoquinolinyl, 1,2,3-triazolyl, 1-phenyl-1,2,3-triazolyl,and the like.

“Polycarbonate” as used herein can mean an oligomer or polymercomprising residues of one or more polymer structural units, ormonomers, joined by carbonate linkages.

Unless otherwise indicated, each of the foregoing groups can beunsubstituted or substituted, provided that the substitution does notsignificantly adversely affect synthesis, stability, or use of thecompound.

“Thermal stability” as used herein refers to resistance of a polymer tomolecular weight degradation under thermal conditions. Thus, a polymerwith poor thermal stability can show significant molecular weightdegradation under thermal conditions, such as during extrusion, molding,thermoforming, hot-pressing, and like conditions. Molecular weightdegradation can also be manifest through color formation or in thedegradation of other properties such as weatherability, gloss,mechanical properties, or thermal properties. Molecular weightdegradation can also cause significant variation in processingconditions such as melt viscosity changes.

For the recitation of numeric ranges herein, each intervening numbertherebetween with the same degree of precision is explicitlycontemplated. For example, for the range of 6-9, the numbers 7 and 8 arecontemplated in addition to 6 and 9, and for the range 6.0-7.0, thenumber 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 areexplicitly contemplated.

Disclosed are polycarbonate-based blend compositions. The compositionsinclude at least one high heat polycarbonate, which can be referred toherein as “the first polycarbonate.” The compositions include at leastone poly(aliphatic ester)-polycarbonate copolymer. The compositions caninclude one or more additional polycarbonates, which can be referred toherein as “the second polycarbonate,” and the like. The compositions caninclude one or more polyesters, which can be referred to herein as “thefirst polyester,” “the second polyester,” and the like. The compositionscan include one or more additives.

Polycarbonates of the disclosed blend compositions can behomopolycarbonates, copolymers comprising different moieties in thecarbonate units (referred to as “copolycarbonates”), copolymerscomprising carbonate units and other types of polymer units such aspolysiloxane units, polyester units, and combinations thereof.

The polycarbonates can include identical or different repeating unitsderived from one or more monomers (e.g. a second, third, fourth, fifth,sixth, etc., other monomer compound). The monomers of the polycarbonatecan be randomly incorporated into the polycarbonate. For example, apolycarbonate copolymer can be arranged in an alternating sequencefollowing a statistical distribution, which is independent of the moleratio of the structural units present in the polymer chain. A randompolycarbonate copolymer can have a structure, which can be indicated bythe presence of several block sequences (I-I) and (O-O) and alternatesequences (I-O) or (O-I), that follow a statistical distribution. In arandom x:(1−x) copolymer, wherein x is the mole percent of a firstmonomer(s) and 1−x is the mole percent of the monomers, one cancalculate the distribution of each monomer using peak area valuesdetermined by ¹³C nuclear magnetic resonance (NMR) spectroscopy, forexample.

A polycarbonate copolymer can have alternating I and O units(-I-O-I-O-I-O-I-O-), or I and O units arranged in a repeating sequence(e.g. a periodic copolymer having the formula:(I-O-I-O-O-I-I-I-I-O-O-O)n). The polycarbonate copolymer can be astatistical copolymer in which the sequence of monomer residues followsa statistical rule. For example, if the probability of finding a giventype monomer residue at a particular point in the chain is equal to themole fraction of that monomer residue in the chain, then the polymer canbe referred to as a truly random copolymer. The polycarbonate copolymercan be a block copolymer that comprises two or more homopolymer subunitslinked by covalent bonds (-I-I-I-I-I-O-O-O-O-O-). The union of thehomopolymer subunits can require an intermediate non-repeating subunit,known as a junction block. Block copolymers with two or three distinctblocks are called diblock copolymers and triblock copolymers,respectively.

The polycarbonates can include any suitable mole percent (mol %) ofselected monomer units. The polymers can comprise 1 to 99.5 mol %, 5 to95 mol %, 10 to 90 mol %, 15 to 85 mol %, 20 to 80 mol %, 25 to 75 mol%, 30 to 70 mol %, 3% to 65 mol %, 40 to 60 mol %, or 45 to 55 mol % ofa selected monomer unit.

The polycarbonates can have a Tg of greater than or equal to 120° C.,greater than or equal to 125° C., greater than or equal to 130° C.,greater than or equal to 135° C., greater than or equal to 14° C.,greater than or equal to 145° C., greater than or equal to 150° C.,greater than or equal to 155° C., greater than or equal to 160° C.,greater than or equal to 165° C., greater than or equal to 170° C.,greater than or equal to 175° C., greater than or equal to 180° C.,greater than or equal to 185° C., greater than or equal to 190° C.,greater than or equal to 200° C., greater than or equal to 210° C.,greater than or equal to 220° C., greater than or equal to 230° C.,greater than or equal to 24° C., greater than or equal to 250° C.,greater than or equal to 260° C., greater than or equal to 270° C.,greater than or equal to 280° C., greater than or equal to 290° C., orgreater than or equal to 300° C., as measured using a differentialscanning calorimetry method. In any of the foregoing embodiments, the Tgof the polycarbonate can be less than 500° C., or less than 450° C., orless than 400° C., or less than 380° C. In some embodiments the Tg ofthe polycarbonates is 150° C. to 380° C.

The polycarbonates can have a weight average molecular weight (Mw) of1,500 to 150,000 Daltons (Da) [^(±)1,000 Da], 10,000 to 50,000 Da[^(±)1,000 Da], 15,000 to 35,000 Da [^(±)1,000 Da], or 20,000 to 30,000Da [^(±)1,000 Da]. In certain embodiments, the polycarbonates haveweight average molecular weights of 15,000 Da [^(±)1,000 Da], 16,000 Da[^(±)1,000 Da], 17,000 Da [^(±)1,000 Da], 18,000 Da [^(±)1,000 Da],19,000 Da [^(±)1,000 Da], 20,000 Da [^(±)1,000 Da], 21,000 Da [^(±)1,000Da], 22,000 Da [^(±)1,000 Da], 23,000 Da [^(±)1,000 Da], 24,000 Da[^(±)1,000 Da], 25,000 Da [^(±)1,000 Da], 26,000 Da [^(±)1,000 Da],27,000 Da [^(±)1,000 Da], 28,000 Da [^(±)1,000 Da], 29,000 Da [^(±)1,000Da], 30,000 Da [^(±)1,000 Da], 31,000 Da [^(±)1,000 Da], 32,000 Da[^(±)1,000 Da], 33,000 Da [^(±)1,000 Da], 34,000 Da [1,000 Da], or35,000 Da [^(±)1,000 Da]. In any of the foregoing embodiments, the Mw ofthe polycarbonate can be less than 100,000 Da, or less than 75,000 Da,or less than 50,000 Da. In some embodiments the Mw of the polycarbonatescan be 15,000 to 50,000 Da. Molecular weight determinations can beperformed using gel permeation chromatography (GPC), using across-linked styrene-divinylbenzene column and calibrated topolycarbonate references using a UV-VIS detector set at 254 nm. Samplescan be prepared at a concentration of 1 mg/ml, and eluted at a flow rateof 1.0 ml/min.

The polycarbonates can have a polydispersity index (PDI) of 1.0 to 10.0,2.0 to 7.0, or 2.0 to 6.0. In certain embodiments, the polycarbonateshave PDIs of 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00,or 7.50. In certain embodiments, the polycarbonates have a PDI of 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. In certainembodiments, the polycarbonates have a PDI of 2.2 or 2.3.

The polycarbonates can have a biocontent of 2 to 90 weight percent (wt%); 5 to 25 wt %; 10 to 30 wt %; 15 to 35 wt %; 20 to 40 wt %; 25 to 45wt %; 30 to 50 wt %; 35 to 55 wt %; 40 to 60 wt %; 45 to 65 wt %; 55 to70% wt %; 60 to 75 wt %; 50 to 80 wt %; or 50 to 90 wt %. The biocontentcan be measured according to ASTM D6866.

The term “polycarbonate” and “polycarbonate resin” refers tocompositions having repeating units of formula (1):

wherein each R¹⁰⁰ can independently comprise any suitable organic group,such as an aliphatic, alicyclic, or aromatic group, or any combinationthereof. In certain embodiments certain embodiments, R¹⁰⁰ in thecarbonate units of formula (1) can be a C₆-C₃₆ aromatic group wherein atleast one moiety is aromatic.

The repeating units of formula (1) can be derived from dihydroxycompounds of formula (2):

HO—R¹⁰⁰—OH  (2)

wherein R¹⁰⁰ is as defined above.

The polycarbonate can include repeating units of formula (3):

wherein each of the A¹ and A² is a monocyclic divalent aryl group and Y¹is a bridging group having one or two atoms that separate A¹ and A². Forexample, one atom can separate A¹ from A², with illustrative examples ofthese groups including —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, methylene,cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene,isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecyclidene,cyclododecylidene, and adamantylidene. The bridging group of Y¹ can be ahydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.

The repeating units of formula (3) can be derived from a dihydroxymonomer of formula (4):

HO-A¹-Y¹-A²-OH  (4)

wherein A¹, A², and Y¹ are as defined above.

The polycarbonate can include repeating units of formula (5):

wherein R^(a) and R^(b) are each independently halogen, C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂ alkoxy; p and q are eachindependently 0 to 4; and X^(a) is a bridging group between the twoarylene groups. X^(a) can be a single bond. —O—, —S—, —S(O)—, —S(O)₂—,—C(O)—, or a C₁-C₁₈ organic group. The C₁-C₁₈ organic bridging group canbe cyclic or acyclic, aromatic or non-aromatic, and can optionallyinclude halogens, heteroatoms (e.g., oxygen, nitrogen, sulfur, silicon,or phosphorous), or a combination thereof. The C₁-C₁₈ organic group canbe disposed such that the C₆ arylene groups connected thereto are eachconnected to a common alkylidene carbon or to different carbons of theC₁-C₁₈ organic bridging group. The bridging group X^(a) and thecarbonate oxygen atoms of each C₆ arylene group can be disposed ortho,meta, or para (specifically para) to each other on the C₆ arylene group.Exemplary X^(a) groups include, but are not limited to, methylene,ethylidene, neopentylidene, isopropylidene, cyclohexylmethylidene,1,1-ethene, 2-[2.2.1]-bicycloheptylidene, cyclohexylidene,cyclopentylidene, cyclododecylidene, and adamantylidene.

In certain embodiments, p and q are each 1; R^(a) and R^(b) are each aC₁-C₃ alkyl group, specifically methyl, disposed meta to the oxygen oneach ring; and X^(a) is isopropylidene. In certain embodiments, p and qare both 0; and X^(a) is isopropylidene.

In certain embodiments, X^(a) can have formula (6):

wherein R^(c) and R^(d) are each independently hydrogen, halogen, alkyl(e.g., C₁-C₁₂ alkyl), cycloalkyl (e.g., C₃-C₁₂ cycloalkyl),cycloalkylalkyl (e.g., C₃-C₁-cycloalkyl-C₁-C₆-alkyl), aryl (e.g., C₆-C₁₂aryl), arylalkyl (e.g., C₆-C₁₂-aryl-C₁-C₆-alkyl), heterocyclyl (e.g.,five- or six-membered heterocyclyl having one, two, three, or fourheteroatoms independently selected from nitrogen, oxygen, and sulfur),heterocyclylalkyl (e.g., five- or six-memberedheterocyclyl-C₁-C₆-alkyl), heteroaryl (e.g., five- or six-memberedheteroaryl having one, two, three, or four heteroatoms independentlyselected from nitrogen, oxygen, and sulfur), or heteroarylalkyl (e.g.,five- or six-membered heteroaryl-C₁-C₆-alkyl), wherein said alkyl,cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl are eachindependently unsubstituted or substituted (e.g., substituted with 1 to3 substituents independently selected from the group consisting of —OH,—NH₂, —NO₂, —CN, halo, C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,halo-C₁-C₄-alkyl, halo-C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl,amino-C₁-C₄-alkyl, C₁-C₄-alkylamino-C₁-C₄-alkyl,di(C₁-C₄-alkyl)amino-C₁-C₄-alkyl, azido-C₁-C₄-alkyl, cyano-C₁-C₄-alkyl,C₁-C₄-alkoxy, halo-C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy,C₂-C₄-alkenyl, and C₂-C₄-alkynyl). In certain embodiments, R^(c) andR^(d) are each independently hydrogen or C₁-C₈ alkyl. In certainembodiments, R^(c) and R^(d) are each methyl. Exemplary groups offormula (6) include, but are not limited to, methylene, ethylidene,neopentylidene, and isopropylidene.

In certain embodiments, X^(a) can have formula (7):

wherein R^(e) is a divalent C₁-C₃₁ group. In certain embodiments, R^(e)is a divalent hydrocarbyl (e.g., a C₁₂-C₃₁ hydrocarbyl), acycloalkylidene (e.g., a C₅-C₁₈ cycloalkylidene), a cycloalkylene (e.g.,a C₅-C₁₈ cycloalkylene), a heterocycloalkylidene (e.g., a C₃-C₁₈heterocycloalkylidene), or a group of the formula —B¹-G-B²- wherein B¹and B² are the same or different alkylene group (e.g., a C₁-C₆ alkylenegroup) and G is a cycloalkylidene group (e.g., a C₃-C₁₂ cycloalkylidenegroup) or an arylene group (e.g., a C₆-C₁₆ arylene group), wherein saidhydrocarbyl, cycloalkylidene, cycloalkylene, and heterocycloalkylideneare each independently unsubstituted or substituted (e.g., substitutedwith 1 to 3 substituents independently selected from the groupconsisting of —OH, —NH₂, —NO₂, —CN, halo, C₁-C₄-alkyl,C₁-C₄-alkoxy-C₁-C₄-alkyl, halo-C₁-C₄-alkyl,halo-C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, amino-C₁-C₄-alkyl,C₁-C₄-alkylamino-C₁-C₄-alkyl, di(C₁-C₄-alkyl)amino-C₁-C₄-alkyl,azido-C₁-C₄-alkyl, cyano-C₁-C₄-alkyl, C₁-C₄-alkoxy, halo-C₁-C₄-alkoxy,C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₂-C₄-alkenyl, and C₂-C₄-alkynyl). Exemplarygroups of formula (7) include, but are not limited to,2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene,cyclododecylidene, and adamantylidene.

The repeating structural units of formula (5) can be derived from adihydroxy monomer unit of formula (8):

wherein X^(a), R^(a), R^(b), p, and q are as defined above. In certainembodiments, p and q are both 0, and X^(a) is isopropylidene.

The polycarbonate can include repeating units of formula (9), formula(10), formula (11), or a combination thereof:

wherein R¹³ at each occurrence is independently a halogen or a C₁-C₆alkyl group; R¹⁴ is independently a C₁-C₆ alkyl, phenyl, or phenylsubstituted with up to five halogens or C₁-C₆ alkyl groups; R^(a) andR^(b), at each occurrence, are each independently a halogen, C₁-C₁₂alkyl, C₁-C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂ alkoxy; c isindependently 0 to 4; and p and q are each independently 0 to 4. In aspecific embodiment, R¹⁴ is a C₁-C₆ alkyl or phenyl group. In stillanother embodiment, R¹⁴ is a methyl or phenyl group. In another specificembodiment, c is 0; p is 0; and q is 0.

The repeating structural units of formula (9) can be derived from adihydroxy monomer unit of formula (12); the repeating structural unitsof formula (10) can be derived from a dihydroxy monomer unit of formula(13); and the repeating structural units of formula (11) can be derivedfrom a dihydroxy monomer unit of formula (14):

wherein R^(a), R^(b), R¹³, c, p, and q are as defined above. Suchdihydroxy compounds can be useful for high heat applications.

The dihydroxy compound of formula (12) can have formula (15), which canbe useful for high heat applications:

(also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one(PPPBP)).

The polycarbonate can include repeating units of formula (16):

wherein R^(a) and R^(b) are each independently halogen, C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂ alkoxy; R^(g) isindependently C₁-C₁₂ alkyl or halogen, or two R^(g) groups together withthe carbon atoms to which they are attached can form a four-, five, orsix-membered cycloalkyl group; p and q are each independently 0 to 4;and t is 0 to 10. R^(a) and R^(b) can be disposed meta to thecyclohexylidene bridging group. The substituents R^(a), R^(b) and R^(g)can, when comprising an appropriate number of carbon atoms, be straightchain, cyclic, bicyclic, branched, saturated, or unsaturated. In oneexample, R^(a), R^(b) and R^(g) are each independently C₁-C₄ alkyl, pand q are each 0 or 1, and t is 0 to 5. In another example, R^(a), R^(b)and R^(g) are each methyl, p and q are each 0 or 1, and t is 0 or 3. Thecyclohexylidene-bridged bisphenol can be the reaction product of twomoles of o-cresol with one mole of cyclohexanone. In another example,the cyclohexylidene-bridged bisphenol can be the reaction product of twomoles of a cresol with one mole of a hydrogenated isophorone (e.g.,1,1,3-trimethyl-3-cyclohexane-5-one). Such cyclohexane-containingbisphenols, for example the reaction product of two moles of a phenolwith one mole of a hydrogenated isophorone, are useful for makingpolycarbonate polymers with high Tgs and high heat distortiontemperatures. Cyclohexyl bisphenol-containing polycarbonates, or acombination comprising at least one of the foregoing with otherbisphenol polycarbonates, are supplied by Bayer Co. under the APEC tradename.

The repeating structural units of formula (16) can be derived from adihydroxy monomer unit of formula (17):

wherein R^(a), R^(b), R^(g), p, q, and t are as defined above.

The dihydroxy compound of formula (17) can have formula (18) (also knownas 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC)), or of formula(19) (also known as bisphenol isophorone), or of formula (20), any ofwhich can be useful for high heat applications:

The polycarbonate can include repeating units of formula (21):

wherein R^(r), R^(p), R^(q) and R^(t) are each independently hydrogen,halogen, oxygen, or a C₁-C₁₂ organic group; R^(a) and R^(b) are eachindependently halogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, (C₃-C₈ cycloalkyl,or C₁-C₁₂ alkoxy; I is a direct bond, a carbon, or a divalent oxygen,sulfur, or —N(Z)— where Z is hydrogen, halogen, hydroxy, C₁-C₁₂ alkyl,C₁-C₁₂ alkoxy, C₆-C₁₂ aryl, or C₁-C₁₂ acyl; h is 0 to 2, j is 1 or 2, iis an integer of 0 or 1, k is an integer of 0 to 3, p is an integer of 0to 4, and q is an integer 0 to 4, with the proviso that at least two ofR^(r), R^(p), R^(q) and R^(t) taken together are a fused cycloaliphatic,aromatic, or heteroaromatic ring. It will be understood that where thefused ring is aromatic, the ring as shown in formula (21) will have anunsaturated carbon-carbon linkage where the ring is fused. When i is 0,h is 0, and k is 1, the ring as shown in formula (21) contains 4 carbonatoms; when i is 0, h is 0, and k is 2, the ring as shown contains 5carbon atoms, and when i is 0, h is 0, and k is 3, the ring contains 6carbon atoms. In one example, two adjacent groups (e.g., R^(q) and R^(t)taken together) form an aromatic group, and in another embodiment, R^(q)and R^(t) taken together form one aromatic group and R^(r) and R^(p)taken together form a second aromatic group. When R^(q) and R^(t) takentogether form an aromatic group, R^(p) can be a double-bonded oxygenatom, i.e., a ketone.

The repeating structural units of formula (21) can be derived from adihydroxy monomer unit of formula (22):

wherein R^(a), R^(b), R^(r), R^(p), R^(q), R^(t), I, h, i, j, k, p, andq are as defined above.

The polycarbonate can include repeating units of formula (23):

wherein R^(a) and R^(b) are each independently halogen, C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂ alkoxy; and p and q are eachindependently 0 to 4. In certain embodiments, at least one of each ofR^(a) and R^(b) are disposed meta to the cycloalkylidene bridging group.In certain embodiments, R^(a) and R^(b) are each independently C₁-C₃alkyl; and p and q are each 0 or 1. In certain embodiments, R^(a) andR^(b) are each methyl; and p and q are each 0 or 1.

The repeating structural units of formula (23) can be derived from adihydroxy monomer unit of formula (24):

wherein R^(a), R^(b), p, and q are as defined above. Such dihydroxycompounds that might impart high Tgs to the polycarbonate as acopolycarbonate are described in U.S. Pat. No. 7,244,804.

The dihydroxy compound of formula (24) can have formula (25), which canbe useful for high heat applications:

(also known as 9,9-bis(4-hydroxyphenyl)fluorene).

The polycarbonate can include repeating units of formula (26):

wherein R^(a) and R^(b) are each independently halogen, C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂ alkoxy; and p and q are eachindependently 0 to 4. In certain embodiments, at least one of each ofR^(a) and R^(b) are disposed meta to the cycloalkylidene bridging group.In certain embodiments, R^(a) and R^(b) are each independently C₁-C₃alkyl; and p and q are each 0 or 1. In certain embodiments, R^(a) andR^(b) are each methyl; and p and q are each 0 or 1.

The repeating structural units of formula (26) can be derived from adihydroxy monomer unit of formula (27):

wherein R^(a), R^(b), p, and q are as defined above. Such dihydroxycompounds that might impart high Tgs to the polycarbonate are describedin U.S. Pat. No. 7,112,644 and U.S. Pat. No. 3,516,968.

The dihydroxy compound of formula (27) can have formula (28), which canbe useful for high heat applications:

(also known as 2,2-bis(4-hydroxyphenyl)adamantane).

A dihydroxy compound of formula (29) can be useful for high heatapplications:

(also known as 4,4′-(1-phenylethane-1,1-diyl)diphenol (bisphenol-AP) or1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane).

A dihydroxy compound of formula (30) can be useful for high heatapplications:

(also known as 6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane).

A dihydroxy compound of formula (31) can be useful for high heatapplications:

(also known as4,4′-(3,3-dimethyl-2,2-dihydro-1H-indene-1,1-diyl)diphenol).

Exemplary monomers for inclusion in the polycarbonate include, but arenot limited to, 4,4′-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)acetonitrile, bis(4-hydroxyphenyl)phenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane,1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane(“bisphenol-A” or “BPA”),2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,2,2-bis(4-hydroxy-2-methylphenyl)propane,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxyphenyl)butane,3,3-bis(4-hydroxyphenyl)-2-butanone, 1,1-bis(4-hydroxyphenyl)isobutene,trans-2,3-bis(4-hydroxyphenyl)-2-butene,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)cyclododecane,2,2-bis(4-hydroxyphenyl)adamantane, (alpha,alpha′-bis(4-hydroxyphenyl)toluene, 4,4′-dihydroxybenzophenone,2,7-dihydroxypyrene, bis(4-hydroxyphenyl)ether, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide,bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone,bis(4-hydroxyphenyl)diphenylmethane, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene,2,7-dihydroxycarbazole, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine(also referred to as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-oneor “PPPBP”), 9,9-bis(4-hydroxyphenyl)fluorene, and bisphenol isophorone(also referred to as 4,4′-(3,3,5-trimethylcyclohexane-1,1-diyl)diphenolor “BPI”), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (“DMBPC”),tricyclopentadienyl bisphenol (also referred to as 4,4′-(octahydro-lH-4,7-methanoindene-5,5-diyl)diphenol),2,2-bis(4-hydroxyphenyl)adamantane (“BCF”),1,1-bis(4-hydroxyphenyl)-1-phenyl ethane (“BPAP”), and3,3-bis(4-hydroxyphenyl)phthalide, or any combination thereof.

Exemplary monomers useful for increasing the Tg of the polycarbonateinclude, but are not limited to, bis(4-hydroxyphenyl)diphenylmethane,1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene,2,7-dihydroxycarbazole, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine(also referred to as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-oneor “PPPBP”), 9,9-bis(4-hydroxyphenyl)fluorene, and bisphenol isophorone(also referred to as 4,4′-(3,3,5-trimethylcyclohexane-1,1-diyl)diphenolor “BPI”), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (“DMBPC”),tricyclopentadienyl bisphenol (also referred to as4,4′-(octahydro-1H-4,7-methanoindene-5,5-diyl)diphenol),2,2-bis(4-hydroxyphenyl)adamantane (“BCF”),1,1-bis(4-hydroxyphenyl)-1-phenyl ethane (“BPAP”), and3,3-bis(4-hydroxyphenyl)phthalide, or any combination thereof.

Other dihydroxy monomer units that can be used include aromaticdihydroxy compounds of formula (32):

wherein each R^(h) is independently a halogen atom, a C₁-C₁₀ hydrocarbylsuch as a C₁-C₁₀ alkyl group, or a halogen substituted C₁-C₁₀hydrocarbyl such as a halogen-substituted C₁-C₁₀ alkyl group, and n is 0to 4. The halogen, when present, is usually bromine.

Examples of aromatic dihydroxy compounds represented by formula (31)include, but are not limited to, resorcinol, substituted resorcinolcompounds (e.g., 5-methyl resorcinol, 5-ethyl resorcinol, 5-propylresorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenylresorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol,2,4,5,6-tetrabromo resorcinol), catechol, hydroquinone, substitutedhydroquinones (e.g., 2-methyl hydroquinone, 2-ethyl hydroquinone,2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone,2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromo hydroquinone, and the like, as well ascombinations thereof.

The compositions can include one or more polyester-polycarbonatecopolymers. The polyester-polycarbonate can comprise repeating esterunits of formula (33):

wherein O-D-O of formula (33) is a divalent group derived from adihydroxy compound, and D can be, for example, one or more alkylcontaining C₆-C₂₀ aromatic group(s), or one or more C₆-C₂₀ aromaticgroup(s), a C₂-C₁₀ alkylene group, a C₆-C₂₀ alicyclic group, a C₆-C₂₀aromatic group or a polyoxyalkylene group in which the alkylene groupscontain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms, 1)can be a C₂-C₃₀ alkylene group having a straight chain, branched chain,or cyclic (including polycyclic) structure. O-D-O can be derived from acompound of formula (2), as described above. O-D-O can be derived froman aromatic dihydroxy compound of formula (4), as described above. O-D-Ocan be derived from an aromatic dihydroxy compound of formula (8), asdescribed above.

The molar ratio of ester units to carbonate units in thepolyester-polycarbonates can vary broadly, for example 1:99 to 99:1,specifically 10:90 to 90:10, more specifically 25:75 to 75:25,optionally expanded depending on the desired properties of the finalcomposition.

T of formula (33) can be a divalent group derived from a dicarboxylicacid, and can be, for example, a C₂-C₁₀ alkylene group, a C₆-C₂₀alicyclic group, a C₆-C₂₀ alkyl aromatic group, a C₆-C₂₀ aromatic group,or a C₆-C₃₆ divalent organic group derived from a dihydroxy compound orchemical equivalent thereof. T can be an aliphatic group, wherein themolar ratio of carbonate units to ester units of formula (33) in thepoly(aliphatic ester)-polycarbonate copolymer is from 99:1 to 60:40; and0.01 to 10 weight percent, based on the total weight of the polymercomponent, of a polymeric containing compound. T can be derived from aC₆-C₂₀ linear aliphatic alpha-omega (α-ω) dicarboxylic ester.

Diacids from which the T group in the ester unit of formula (33) isderived include aliphatic dicarboxylic acids having from 6 to 36 carbonatoms, optionally from 6 to 20 carbon atoms. The C₆-C₂₀ linear aliphaticalpha-omega (α-ω) dicarboxylic acids can be adipic acid, sebacic acid,3,3-dimethyl adipic acid, 3,3,6-trimethyl sebacic acid,3,3,5,5-tetramethyl sebacic acid, azelaic acid, dodecanedioic acid,dimer acids, cyclohexane dicarboxylic acids, dimethyl cyclohexanedicarboxylic acid, norbornane dicarboxylic acids, adamantanedicarboxylic acids, cyclohexene dicarboxylic acids, or C₁₄, C₁₈ and C₂₀diacids.

The ester units of the polyester-polycarbonates of formula (33) can befurther described by formula (34), wherein T is (CH₂)_(m), where m is 4to 40 or optionally m is 4 to 18. m can be 8 to 10.

Saturated aliphatic alpha-omega dicarboxylic acids can be adipic acid,sebacic or dodecanedioic acid. Sebacic acid is a dicarboxylic acidhaving the following formula (35):

Sebacic acid has a molecular mass of 202.25 Da, a density of 1.209 g/cm³(at 25° C.), and a melting point of 294.4° C. at 100 mmHg. Sebacic acidis extracted from castor bean oil found in naturally occurring castorbeans.

The poly(aliphatic ester)-polycarbonate can include less than or equalto 25 mol % of the aliphatic dicarboxylic acid unit. The poly(aliphaticester)-polycarbonate can comprise units of formula (34) in an amount of0.5 to 10 mol %, specifically 1 to 9 mol %, and more specifically 3 to 8mol %, based on the total amount of the poly(aliphaticester)-polycarbonate.

The poly(aliphatic ester)-polycarbonate can be a copolymer of aliphaticdicarboxylic acid units and carbonate units. The poly(aliphaticester)-polycarbonate is shown in formula (36):

where each R³ is independently derived from a dihydroxyaromatic compoundof formula (8) or (32), m is 4 to 18, and x and y each represent averageweight percentages of the poly(aliphatic ester)-polycarbonate where x+yis 100.

A specific embodiment of the poly(aliphatic ester)-polycarbonate isshown in formula (37), where m is 4 to 18 and x and y are as defined forformula (36)

In some embodiments, a useful poly(aliphatic ester)-polycarbonatecopolymer comprises sebacic acid ester units and bisphenol A carbonateunits (formula (37), where m is 8).

Desirably, the poly(aliphatic ester)-polycarbonate has a Tg of 100 to145° C.

Other examples of aromatic dicarboxylic acids that can be used toprepare the polyester units include isophthalic, terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, and combinations comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids can be terephthalic acid, isophthalic acid,naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, orcombinations thereof. A specific dicarboxylic acid comprises acombination of isophthalic acid and terephthalic acid wherein the weightratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.

D of the repeating units of formula (33) can also be a C₂-C₆ alkylenegroup and T can be p-phenylene, m-phenylene, naphthalene, a divalentcycloaliphatic group, or a combination thereof. This class of polyesterincludes the poly(alkylene terephthalates).

Mixtures of the diacids can also be employed. It should be noted thatalthough referred to as diacids, any ester precursor could be employedsuch as acid halides, specifically acid chlorides, and diaromatic estersof the diacid such as diphenyl, for example the diphenyl ester ofsebacic acid. With reference to the diacid carbon atom number earliermentioned, this does not include any carbon atoms which can be includedin the ester precursor portion, for example diphenyl. It can bedesirable that at least four, five or six carbon bonds separate the acidgroups. This can reduce the formation of undesirable and unwanted cyclicspecies.

The polyester unit of a polyester-polycarbonate can be derived from thereaction of a combination of isophthalic and terephthalic diacids (orderivatives thereof) with resorcinol. In another embodiment, thepolyester unit of a polyester-polycarbonate can be derived from thereaction of a combination of isophthalic acid and terephthalic acid withBPA. In some embodiments, the polycarbonate units can be derived fromBPA. In another specific embodiment, the polycarbonate units can bederived from resorcinol and BPA in a molar ratio of resorcinol carbonateunits to BPA carbonate units of 1:99 to 99:1.

In certain embodiments, the polyester-polycarbonate is a copolymer offormula (38):

wherein the polyester-polycarbonate includes bisphenol A carbonateblocks, and polyester blocks made of a copolymer of bisphenol A withisophthalate, terephthalate or a combination of isophthalate andterephthalate. Further in the polyester-polycarbonate (38), x and yrepresent the respective parts by weight of the aromatic carbonate unitsand the aromatic ester units based on 100 parts total weight of thecopolymer. Specifically, x, the carbonate content, is from more thanzero to 80 wt %, from 5 to 70 wt %, still more specifically from 5 to 50wt %, and y, the aromatic ester content, is 20 to less than 100 wt %,specifically 30 to 95 wt %, still more specifically 50 to 95 wt %, eachbased on the total weight of units x+y. The weight ratio of terephthalicacid to isophthalic acid can be in the range of from 5:95 to 95:5.Polyester-polycarbonate (38) comprising 35 to 45 wt % of carbonate unitsand 55 to 65 wt % of ester units, wherein the ester units have a molarratio of isophthalate to terephthalate of 45:55 to 55:45 can be referredto as PCE; and copolymers comprising 15 to 25 wt % of carbonate unitsand 75 to 85 wt % of ester units having a molar ratio of isophthalate toterephthalate from 98:2 to 88:12 can be referred to as PPC. In theseembodiments the PCE or PPC can be derived from reaction of bisphenol-Aand phosgene with iso- and terephthaloyl chloride, and can have anintrinsic viscosity of 0.5 to 0.65 deciliters per gram (measured inmethylene chloride at a temperature of 25° C.).

Useful polyesters can include aromatic polyesters, poly(alkylene esters)including poly(alkylene arylates), and poly(cycloalkylene diesters).Aromatic polyesters can have a polyester structure according to formula(33), wherein D and T are each aromatic groups as described hereinabove.Useful aromatic polyesters can include, for example,poly(isophthalate-terephthalate-resorcinol) esters,poly(isophthalate-terephthalate-bisphenol-A) esters,poly[(isophthalate-terephthalate-resorcinol)ester-co-(isophthalate-terephthalate-bisphenol-A)] ester, or acombination comprising at least one of these.

End capping agents can be incorporated into the polycarbonates.Exemplary chain-stoppers include certain monophenolic compounds (i.e.,phenyl compounds having a single free hydroxy group), monocarboxylicacid chlorides, monocarboxylic acids, and monochloroformates. Phenolicchain-stoppers are exemplified by phenol and C₁-C₂₂ alkyl-substitutedphenols such as p-cumyl-phenol (PCP), resorcinol monobenzoate, andp-tertiary-butylphenol, cresol, and monoethers of diphenols, such asp-methoxyphenol. Exemplary chain-stoppers also include cyanophenols,such as for example, 4-cyanophenol, 3-cyanophenol, 2-cyanophenol, andpolycyanophenols. Alkyl-substituted phenols with branched chain alkylsubstituents having 8 to 9 carbon atoms can be specifically be used.

Endgroups can be derived from the carbonyl source (i.e., the diarylcarbonate), from selection of monomer ratios, incomplete polymerization,chain scission, and the like, as well as any added endcapping groups,and can include derivatizable functional groups such as hydroxy groups,carboxylic acid groups, or the like. In some embodiments, the endgroupof a polycarbonate can comprise a structural unit derived from a diarylcarbonate, where the structural unit can be an endgroup. In a furtherembodiment, the endgroup is derived from an activated carbonate. Suchendgroups can derive from the transesterification reaction of the alkylester of an appropriately substituted activated carbonate, with ahydroxy group at the end of a polycarbonate polymer chain, underconditions in which the hydroxy group reacts with the ester carbonylfrom the activated carbonate, instead of with the carbonate carbonyl ofthe activated carbonate. In this way, structural units derived fromester containing compounds or substructures derived from the activatedcarbonate and present in the melt polymerization reaction can form esterendgroups. In some embodiments, the ester endgroup derived from asalicylic ester can be a residue of bis(methyl salicyl) carbonate (BMSC)or other substituted or unsubstituted bis(alkyl salicyl) carbonate suchas bis(ethyl salicyl) carbonate, bis(propyl salicyl) carbonate,bis(phenyl salicyl) carbonate, bis(benzyl salicyl) carbonate, or thelike. In a specific embodiment, where BMSC is used as the activatedcarbonyl source, the endgroup is derived from and is a residue of BMSC,and is an ester endgroup derived from a salicylic acid ester as is knownin the art.

The polycarbonates can be manufactured by processes such as interfacialpolymerization, melt polymerization, and reactive extrusion. High Tgcopolycarbonates are generally manufactured using interfacialpolymerization.

Polycarbonates produced by interfacial polymerization can have an arylhydroxy end-group content of 150 parts per million (ppm) or less, 100ppm or less, or 50 ppm or less. Polycarbonates produced by meltpolymerization can have an aryl hydroxy end-group content of greaterthan or equal to 350 ppm, greater than or equal to 400 ppm, greater thanor equal to 450 ppm, greater than or equal to 500 ppm, greater than orequal to 550 ppm, greater than or equal to 600 ppm, greater than orequal to 650 ppm, greater than or equal to 700 ppm, greater than orequal to 750 ppm, greater than or equal to 800 ppm, or greater than orequal to 850 ppm.

Reaction conditions for interfacial polymerization can vary. Anexemplary process generally involves dissolving or dispersing one ormore dihydric phenol reactants, such as BPA, in aqueous caustic soda orpotash, adding the resulting mixture to a water-immiscible solventmedium (e.g., methylene chloride), and contacting the reactants with acarbonate precursor (e.g., phosgene) in the presence of a catalyst suchas, for example, a tertiary amine (e.g., triethylamine) or a phasetransfer catalyst, under controlled pH conditions, e.g., 8 to 11. Themost commonly used water immiscible solvents include methylene chloride,1,2-dichloroethane, chlorobenzene, toluene, and the like.

Exemplary carbonate precursors can include, for example, a carbonylhalide such as carbonyl dibromide or carbonyl dichloride (also known asphosgene), or a haloformate such as a bishaloformate of a dihydricphenol (e.g., the bischloroformate of BPA, hydroquinone, or the like) ora glycol (e.g., the bishaloformate of ethylene glycol, neopentyl glycol,polyethylene glycol, or the like). Combinations comprising at least oneof the foregoing types of carbonate precursors can also be used. Incertain embodiments, the carbonate precursor is phosgene, a triphosgene,diacyl halide, dihaloformate, dicyanate, diester, diepoxy,diarylcarbonate, dianhydride, dicarboxylic acid, diacid chloride, or anycombination thereof. An interfacial polymerization reaction to formcarbonate linkages can use phosgene as a carbonate precursor, and isreferred to as a phosgenation reaction.

Among tertiary amines that can be used are aliphatic tertiary aminessuch as triethylamine, tributylamine, cycloaliphatic amines such asN,N-diethyl-cyclohexylamine and aromatic tertiary amines such asN,N-dimethylaniline.

Among the phase transfer catalysts that can be used are catalysts of theformula (R³⁰)₄Q⁺X, wherein each R³⁰ is the same or different, and is aC₁-C₁₀ alkyl group; Q is a nitrogen or phosphorus atom; and X is ahalogen atom, C₁-C₈ alkoxy group, or C₆-C₁₈ aryloxy group. Exemplaryphase transfer catalysts include, for example, [CH₃(CH₂)₃]₄NX,[CH₃(CH₂)₃]₄PX, [CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX,CH₃[CH₃(CH₂)₃]₃NX, and CH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁-C₈alkoxy group or a C₆-C₁₈ aryloxy group. An effective amount of a phasetransfer catalyst can be 0.1 to 10 wt % based on the weight of bisphenolin the phosgenation mixture. For example, an effective amount of phasetransfer catalyst can be 0.5 to 2 wt % based on the weight of bisphenolin the phosgenation mixture.

Specifically, polyester-polycarbonates, including the poly(aliphaticester)-polycarbonates, can be prepared by interfacial polymerization.Rather than utilizing the dicarboxylic acid (such as the alpha, omegaC₆₋₂₀ aliphatic dicarboxylic acid) per se, it is possible, and sometimeseven preferred, to employ the reactive derivatives of the dicarboxylicacid, such as the corresponding dicarboxylic acid halides, and inparticular the acid dichlorides and the acid dibromides. Thus, forexample instead of using isophthalic acid, terephthalic acid, or acombination comprising at least one of the foregoing (for poly(arylateester)-polycarbonates), it is possible to employ isophthaloyldichloride, terephthaloyl dichloride, and a combination comprising atleast one of the foregoing. Similarly, for the poly(aliphaticester)-polycarbonates, it is possible, and even desirable, to use forexample acid chloride derivatives such as a C₆ dicarboxylic acidchloride (adipoyl chloride), a C₁₀ dicarboxylic acid chloride (sebacoylchloride), or a C₁₂ dicarboxylic acid chloride (dodecanedioyl chloride).The dicarboxylic acid or reactive derivative can be condensed with thedihydroxyaromatic compound in a first condensation, followed by in situphosgenation to generate the carbonate linkages with thedihydroxyaromatic compound. Alternatively, the dicarboxylic acid orderivative can be condensed with the dihydroxyaromatic compoundsimultaneously with phosgenation.

The polymers can be manufactured using a reactive extrusion process. Forexample, a poly(aliphatic ester)-polycarbonate can be modified toprovide a reaction product with a higher flow by treatment using aredistribution catalyst under conditions of reactive extrusion. Forexample, a poly(aliphatic ester)-polycarbonate with an melt volume flowrate (MVR) of less than 13 cc/10 min when measured at 250° C., under aload of 1.2 kg, can be modified to provide a reaction product with ahigher flow (e.g., greater than or equal to 13 cc/10 min when measuredat 250° C., under a load of 1.2 kg), by treatment using a redistributioncatalyst under conditions of reactive extrusion. During reactiveextrusion, the redistribution catalyst can be injected into the extruderbeing fed with the poly(aliphatic ester)-polycarbonate, and optionallyone or more additional components.

The redistribution catalyst can be included in the extrusion process insmall amounts of less than or equal to 400 ppm by weight, for example.The redistribution catalyst can be present in amounts of from 0.01 to0.05 parts per hundred (pph), from 0.1 to 0.04 pph, from 0.02 to 0.03pph, from 0.1 to 1 pph, from 1 to 500 pph, from 100 to 400 pph, from 300to 400 pph, from 100 to 400 ppm, from 200 to 300 ppm, or from 1 to 300ppm by weight based on the weight of the poly(aliphaticester)-polycarbonate. The redistribution catalyst can be present in anamount of 40 to 120 ppm, specifically 40 to 110 ppm, and morespecifically 40 to 100 ppm, by weight based on the weight of thepoly(aliphatic ester)-polycarbonate.

The redistribution catalyst can be injected into the extruder as adiluted aqueous solution. For example, the redistribution catalyst canbe a 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%,75%, 80%, 85%, 90%, 95%, or 99% solution. The redistribution catalystcan be diluted in water.

Examples of redistribution catalysts include a tetraalkylphosphoniumhydroxide, a tetraalkylphosphonium alkoxide, a tetraalkylphosphoniumaryloxide, a tetraalkylphosphonium carbonate, a tetraalkylammoniumhydroxide, a tetraalkylammonium carbonate, a tetraalkylammoniumphosphite, a tetraalkylammonium acetate, or a combination comprising atleast one of the foregoing catalysts, wherein each alkyl isindependently a C₁₋₆ alkyl. Particularly useful redistribution catalystsinclude a tetra C₁₋₆ alkylphosphonium hydroxide, a C₁₋₆ alkylphosphonium phenoxide, or a combination comprising one or more of theforegoing catalysts. An exemplary redistribution catalyst istetra-n-butylphosphonium hydroxide. In certain embodiments, theredistribution catalyst can not react with epoxy.

The polycarbonates can be prepared by a melt polymerization process.Generally, in the melt polymerization process, polycarbonates areprepared by co-reacting, in a molten state, the dihydroxy reactant(s)(e.g., bisphenols, aromatic dihydroxy compounds, aliphatic diols,aliphatic diacids, and any additional dihydroxy compound) and a diarylcarbonate ester, such as diphenyl carbonate, or more specifically insome embodiments, an activated carbonate such as bis(methyl salicyl)carbonate, in the presence of a transesterification catalyst. Thereaction can be carried out in typical polymerization equipment, such asone or more continuously stirred tank reactors (CSTR's), plug flowreactors, wire wetting fall polymerizers, free fall polymerizers, wipedfilm polymerizers, BANBURY® mixers, single or twin screw extruders, orcombinations of the foregoing. Volatile monohydric phenol is removedfrom the molten reactants by distillation and the polymer is isolated asa molten residue.

A specifically useful melt process for making polycarbonates uses adiaryl carbonate ester having electron-withdrawing substituents on thearyls, which can be referred to herein as an “activated carbmonate.”Examples of specifically useful diaryl carbonate esters with electronwithdrawing substituents include bis(4-nitrophenyl)carbonate,bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methylsalicyl)carbonate, bis(4-methylcarboxylphenyl)carbonate,bis(2-acetylphenyl)carboxylate, bis(4-acetylphenyl)carboxylate, or acombination comprising at least one of the foregoing. Bis(methylsalicyl)carbonate can be used as the activated carbonate in meltpolycarbonate synthesis due to its lower molecular weight and highervapor pressure.

The melt polymerization can include a transesterification catalystcomprising a first catalyst, also referred to herein as an alphacatalyst, comprising a metal cation and an anion. In an aspect, thecation is an alkali or alkaline earth metal comprising Li, Na, K, Cs,Rb, Mg, Ca, Ba, Sr, or a combination comprising at least one of theforegoing. The anion is hydroxide (OH⁻), superoxide (O₂ ⁻), thiolate(HS⁻), sulfide (S₂ ⁻), a C₁-C₂₀ alkoxide, a C₆-C₂₀ aryloxide, a C₁-C₂₀carboxylate, a phosphate including biphosphate, a C₁-C₂₀ phosphonate, asulfate including bisulfate, sulfites including bisulfates andmetabisulfites, a C₁-C₂₀ sulfonate, a carbonate including bicarbonate,or a combination comprising at least one of the foregoing. In anotheraspect, salts of an organic acid comprising both alkaline earth metalions and alkali metal ions can also be used. Salts of organic acidsuseful as catalysts are illustrated by alkali metal and alkaline earthmetal salts of formic acid, acetic acid, stearic acid andethyelenediamine tetraacetic acid. The catalyst can also comprise thesalt of a non-volatile inorganic acid. By “nonvolatile”, it is meantthat the referenced compounds have no appreciable vapor pressure atambient temperature and pressure. In particular, these compounds are notvolatile at temperatures at which melt polymerizations of polycarbonateare typically conducted. The salts of nonvolatile acids are alkali metalsalts of phosphites; alkaline earth metal salts of phosphites; alkalimetal salts of phosphates; and alkaline earth metal salts of phosphates.Exemplary transesterification catalysts include, lithium hydroxide,sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesiumhydroxide, calcium hydroxide, barium hydroxide, lithium formate, sodiumformate, potassium formate, cesium formate, lithium acetate, sodiumacetate, potassium acetate, lithium carbonate, sodium carbonate,potassium carbonate, lithium methoxide, sodium methoxide, potassiummethoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide,lithium phenoxide, sodium phenoxide, potassium phenoxide, sodiumsulfate, potassium sulfate, NaH₂PO₃, NaH₂PO₄, Na₂PO₃, KH₂PO₄, CsH₂PO₄,Cs₂H₂PO₄, Na₂SO₃, Na₂S₂O₅, sodium mesylate, potassium mesylate, sodiumtosylate, potassium tosylate, magnesium disodium ethylenediaminetetraacetate (EDTA magnesium disodium salt), or a combination comprisingat least one of the foregoing. It will be understood that the foregoinglist is exemplary and should not be considered as limited thereto. Insome embodiments, the transesterification catalyst is an alpha catalystconsisting essentially of an alkali or alkaline earth salt. In anexemplary aspect, the transesterification catalyst consists essentiallyof sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, sodium methoxide, potassium methoxide, NaH₂PO₄, or acombination comprising at least one of the foregoing.

The amount of alpha catalyst can vary widely according to the conditionsof the melt polymerization, and can be 0.001 to 500 micromoles (μmol).In an aspect, the amount of alpha catalyst can be 0.01 to 20 μmol,specifically 0.1 to 10 μmol, more specifically 0.5 to 9 μmol, and stillmore specifically 1 to 7 μmol, per mole of aliphatic diol and any otherdihydroxy compound present in the melt polymerization.

A second transesterification catalyst, also referred to herein as a betacatalyst, can optionally be included in the melt polymerization process,provided that the inclusion of such a second transesterificationcatalyst does not significantly adversely affect the desirableproperties of the polymer. Exemplary transesterification catalysts canfurther include a combination of a phase transfer catalyst of formula(R³⁰)₄Q⁺X above, wherein each R³⁰ is the same or different, and is aC₁-C₁₀ alkyl group; Q is a nitrogen or phosphorus atom; and X is ahalogen atom or a C₁-C₈ alkoxy group or C₆-C₁₈ aryloxy group. Exemplaryphase transfer catalyst salts include, for example, [CH₃(CH₂)₃]₄NX,[CH₃(CH₂)₃]₄PX, [CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX,CH₃[CH₃(CH₂)₃]NX, and CH₃[CH₃(CH₂)₂]₃NX, wherein X is C⁻, Br⁻, a C₁-C₈alkoxy group or a C₆-C₁₈ aryloxy group. Examples of suchtransesterification catalysts include tetrabutylammonium hydroxide,methyltributylammonium hydroxide, tetrabutylammonium acetate,tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate,tetrabutylphosphonium phenolate, or a combination comprising at leastone of the foregoing. Other melt transesterification catalysts includealkaline earth metal salts or alkali metal salts. In various aspects,where a beta catalyst is desired, the beta catalyst can be present in amolar ratio, relative to the alpha catalyst, of less than or equal to10, specifically less than or equal to 5, more specifically less than orequal to 1, and still more specifically less than or equal to 0.5. Inother aspects, the melt polymerization reaction disclosed herein usesonly an alpha catalyst as described hereinabove, and is substantiallyfree of any beta catalyst. As defined herein, “substantially free of”can mean where the beta catalyst has been excluded from the meltpolymerization reaction. In some embodiments, the beta catalyst ispresent in an amount of less than 10 ppm, specifically less than 1 ppm,more specifically less than 0.1 ppm, more specifically less than orequal to 0.01 ppm, and more specifically less than or equal to 0.001ppm, based on the total weight of all components used in the meltpolymerization reaction.

Where a combination of alpha and beta catalysts are used in the meltpolymerization, polycarbonate prepared from an activated carbonate cancomprise endgroups in an amount of less than 2,000 ppm, less than 1,500ppm, or less than 1,000 ppm, based on the weight of the polycarbonate.Where only an alpha catalyst is used in the melt polymerization, apolycarbonate prepared from an activated carbonate can compriseendgroups in an amount of less than or equal to 500 ppm, less than orequal to 400 ppm, less than or equal to 300 ppm, or less than or equalto 200 ppm, based on the weight of the polycarbonate.

The reactants for the polymerization reaction using an activatedaromatic carbonate can be charged into a reactor either in the solidform or in the molten form. Initial charging of reactants into a reactorand subsequent mixing of these materials under reactive conditions forpolymerization can be conducted in an inert gas atmosphere such as anitrogen atmosphere. The charging of one or more reactants can also bedone at a later stage of the polymerization reaction. Mixing of thereaction mixture is accomplished by any methods known in the art, suchas by stirring. Reactive conditions include time, temperature, pressureand other factors that affect polymerization of the reactants. Typicallythe activated aromatic carbonate is added at a mole ratio of 0.8 to 1.3,and more preferably 0.9 to 1.3, and all sub-ranges there between,relative to the total moles of monomer unit compounds. In a specificembodiment, the molar ratio of activated aromatic carbonate to monomerunit compounds is 1.013 to 1.29, specifically 1.015 to 1.028.

The melt polymerization reaction can be conducted by subjecting thereaction mixture to a series of temperature-pressure-time protocols.This can involve gradually raising the reaction temperature in stageswhile gradually lowering the pressure in stages. The pressure can bereduced from atmospheric pressure at the start of the reaction to 1millibar (100 Pascals (Pa)) or lower, or to 0.1 millibar (10 Pa) orlower in several steps as the reaction approaches completion. Thetemperature can be varied in a stepwise fashion beginning at atemperature of the melting temperature of the reaction mixture andsubsequently increased to final temperature. The reaction mixture can beheated from room temperature to 150° C. The polymerization reaction canstart at a temperature of 150 to 220° C. The polymerization temperaturecan be up to 220° C. The polymerization reaction can then be increasedto 250° C. and then further increased to a temperature of 320° C., andall sub-ranges there between. The total reaction time can be from 30 to200 minutes and all sub-ranges there between. This procedure willgenerally ensure that the reactants react to give polycarbonates withthe desired molecular weight, Tg and physical properties. The reactionproceeds to build the polycarbonate chain with production ofester-substituted alcohol by-product such as methyl salicylate.Efficient removal of the by-product can be achieved by differenttechniques such as reducing the pressure. Generally the pressure startsrelatively high in the beginning of the reaction and is loweredprogressively throughout the reaction and the temperature is raisedthroughout the reaction.

The progress of the reaction can be monitored by measuring the meltviscosity or the weight average molecular weight of the reaction mixtureusing techniques known in the art such as gel permeation chromatography.These properties can be measured by taking discreet samples or can bemeasured on-line. After the desired melt viscosity or molecular weightis reached, the final polycarbonate product can be isolated from thereactor in a solid or molten form. The polycarbonates can be made in abatch or a continuous process and can be carried out in a solvent freemode. Reactors chosen can be self-cleaning and can be configured tominimize “hot spots.” However, vented extruders similar to those thatare commercially available can be used.

The polycarbonates can be prepared in an extruder in presence of one ormore catalysts, wherein the carbonating agent is an activated aromaticcarbonate. The reactants for the polymerization reaction can be fed tothe extruder in powder or molten form. The reactants can be dry blendedprior to addition to the extruder. The extruder can be equipped withpressure reducing devices (e.g., vents), which serve to remove theactivated phenol by-product and thus drive the polymerization reactiontoward completion. The molecular weight of the polycarbonate productcan, in various aspects, be manipulated by controlling, among otherfactors, the feed rate of the reactants, the type of extruder, theextruder screw design and configuration, the residence time in theextruder, and the reaction temperature and the pressure reducingtechniques present on the extruder. The molecular weight of thepolycarbonate product can also depend upon the structures of thereactants, such as, activated aromatic carbonate, bisphenol compound(s),and the catalyst employed. Many different screw designs and extruderconfigurations are commercially available that use single screws, doublescrews, vents, back flight and forward flight zones, seals, sidestreams,and sizes. A variable for controlling the Mw when using an activatedcarbonate is the ratio diarylcarbonate/diol, specifically BMSC/diol. Alower ratio will give a higher molecular weight.

Decomposition by-products of the reaction that are of low molecularweight can be removed by, for example, devolatilization during reactionor extrusion to reduce the amount of such volatile compounds. Thevolatiles typically removed can include unreacted starting diolmaterials or carbonate precursor materials, but are more specificallythe decomposition products of the melt-polymerization reaction.

In certain embodiments, one or more polycarbonate-polysiloxanecopolymers used in the blend compositions can be produced using acontinuous flow reactor. For example, in a continuous flow reactor(e.g., a tube reactor), a dihydroxy polysiloxane, dissolved in awater-immiscible solvent such as methylene chloride, can be converted bythe action of phosgene and aqueous base into a mixture of mono- andbisphenol chloroformates. The mixture of chloroformates can then betreated with a catalyst, additional aqueous caustic, a dihydroxycompound (e.g., BPA), and a monophenol end capping agent to affordpolycarbonate polysiloxane-copolymers. The chloroformate mixture can betransferred from the tube reactor to an interfacial polymerizationreactor prior to being reacted with the dihydroxy compound (e.g., BPA).

Alternatively, in a continuous flow reactor (e.g., a tube reactor), oneor more dihydroxy compounds (e.g., BPA) can be converted by the actionof phosgene and aqueous base into a mixture of mono-, bis-, andoligomeric chloroformates at a pH of 6 to 8 in the presence of awater-immiscible solvent (e.g., dichloromethane) and a phase transfercatalyst. The reaction mixture can then be treated with a dihydroxypolysiloxane and stirred for 5 to 20 min at pH 10 to 13. Then, moredihydroxy compound (e.g., BPA) can be added and reacted with a carbonateprecursor, such as phosgene at pH 9 to 12. Subsequently, a tertiaryamine catalyst can be added and the mixture again stirred with phosgeneat pH 8 to 12 until the desired polycarbonate-polysiloxane molecularweight is obtained. Again, the chloroformate mixture can be transferredfrom the tube reactor to an interfacial polymerization reactor tocomplete the polymerization process at any point after formation. Themost commonly used water immiscible solvents include methylene chloride,1,2-dichloroethane, chlorobenzene, toluene, and the like.

In certain embodiments, a polysiloxane-polycarbonate copolymer used inthe blend composition can be manufactured using tube reactor processesas described in U.S. Pat. No. 6,833,422 and U.S. Pat. No. 6,723,864.

In certain embodiments, a polysiloxane-polycarbonate copolymer used inthe blend composition can be manufactured as described in U.S. Pat. No.6,870,013 and U.S. Pat. No. 7,232,865.

The compositions can comprise additional components, such as one or moreadditives. Suitable additives include, but are not limited to impactmodifiers, UV stabilizers, colorants, flame retardants, heatstabilizers, plasticizers, lubricants, mold release agents, fillers,reinforcing agents, antioxidant agents, antistatic agents, blowingagents, anti-drip agents, and radiation stabilizers.

Various types of flame retardants can be utilized as additives. In someembodiments, the flame retardant additives include, for example, flameretardant salts such as alkali metal salts of perfluorinated C₁-C₁₆alkyl sulfonates such as potassium perfluorobutane sulfonate (KPFS),potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexanesulfonate, potassium diphenylsulfone sulfonate (KSS), and the like,sodium benzene sulfonate, sodium toluene sulfonate (NATS) and the like;and salts formed by reacting for example an alkali metal or alkalineearth metal (for example lithium, sodium, potassium, magnesium, calciumand barium salts) and an inorganic acid complex salt, for example, anoxo-anion, such as alkali metal and alkaline-earth metal salts ofcarbonic acid, such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, and BaCO₃ orfluoro-anion complex such as Li₃AlF₆, BaSiF₆, KBF₄. K₃AlF₆, KAlF₄,K₂SiF₆, and Na₃AlF₆ or the like. KPFS and KSS and NATS, alone or incombination with other flame retardants, are particularly useful in thecompositions disclosed herein.

The flame retardant additives can include organic compounds that includephosphorus, bromine, and chlorine. Non-brominated and non-chlorinatedphosphorus-containing flame retardants can be used in certainapplications for regulatory reasons, for example organic phosphates andorganic compounds containing phosphorus-nitrogen bonds. One type ofexemplary organic phosphate is an aromatic phosphate of the formula(GO)₃P═O, wherein each G is independently an alkyl, cycloalkyl, aryl,alkylaryl, or arylalkyl group, provided that at least one G is anaromatic group. Two of the G groups can be joined together to provide acyclic group, for example, diphenyl pentaerythritol diphosphate.Exemplary aromatic phosphates include, phenyl bis(dodecyl) phosphate,phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5′-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate,bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate,bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate,bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolyl bis(2,5,5′-trimethylhexyl) phosphate,2-ethylhexyl diphenyl phosphate, or the like. A specific aromaticphosphate is one in which each G is aromatic, for example, triphenylphosphate, tricresyl phosphate, isopropylated triphenyl phosphate, andthe like.

Di- or poly-functional aromatic phosphorus-containing compounds are alsouseful, for example, compounds of the formulas below:

wherein each G¹ is independently a hydrocarbon having 1 to 30 carbonatoms; each G² is independently a hydrocarbon or hydrocarbonoxy having 1to 30 carbon atoms; each X^(a) represents one of the groups of formula(8) above; each X is independently a bromine or chlorine; m is 0 to 4,and n is 1 to 30. Exemplary di- or polyfunctional aromaticphosphorus-containing compounds include resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl) phosphate of bisphenol-A, respectively (BPADP), theiroligomeric and polymeric counterparts, and the like.

Exemplary flame retardant additives containing phosphorus-nitrogen bondsinclude phosphonitrilic chloride, phosphorus ester amides, phosphoricacid amides, phosphonic acid amides, phosphinic acid amides, andtris(aziridinyl) phosphine oxide.

In certain embodiments, the flame retardant is not a bromine or chlorinecontaining composition.

In certain embodiments, the flame retardant is selected from at leastone of potassium perfluorobutane sulfonate, potassium diphenylsulfonesulfonate and an organophosphorus compound. In certain embodiments, theorganophosphorus compound is bisphenol A diphosphate, an oligomericphosphate ester, or a combination thereof.

In certain embodiments, the organophosphorus compound is present in anamount effective to provide 0.1 to 1.5% of phosphorus, 0.1 to 1.2% ofphosphorus, 0.6 to 1.2% of phosphorus, 0.6 to 1.0% of phosphorus, or 0.8to 1.2% of phosphorus, based on the weight of the composition.

Flame retardant additives are generally present in amounts of 0.01 to 10wt %, 0.02 to 5 wt %, 0.1 to 1 wt %, or 0.5 to 1.0 wt % based on 100parts by weight of the polymer component of the thermoplasticcomposition.

Exemplary heat stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- anddi-nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite(Irgafos 168), or the like; phosphonates such as dimethylbenzenephosphonate or the like; phosphates such as trimethyl phosphate, or thelike; or combinations comprising at least one of the foregoing heatstabilizers. In certain embodiments, the heat stabilizer istetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4′diylbisphosphonite.Heat stabilizers are generally used in amounts of 0.0001 to 1 part byweight, based on 100 parts by weight of the polymer component of theblend composition.

Possible fillers or reinforcing agents include, for example, silicatesand silica powders such as aluminum silicate (mullite), syntheticcalcium silicate, zirconium silicate, fused silica, crystalline silicagraphite, natural silica sand, or the like; boron powders such asboron-nitride powder, boron-silicate powders, or the like; oxides suchas TiO₂, aluminum oxide, magnesium oxide, or the like; calcium sulfate(as its anhydride, dihydrate or trihydrate); calcium carbonates such aschalk, limestone, marble, synthetic precipitated calcium carbonates, orthe like; talc, including fibrous, modular, needle shaped, lamellartalc, or the like; wollastonite; surface-treated wollastonite; glassspheres such as hollow and solid glass spheres, silicate spheres,cenospheres, aluminosilicate (armospheres), or the like; kaolin,including hard kaolin, soft kaolin, calcined kaolin, kaolin comprisingvarious coatings known in the art to facilitate compatibility with thepolymeric matrix, or the like; single crystal fibers or “whiskers” suchas silicon carbide, alumina, boron carbide, iron, nickel, copper, or thelike; fibers (including continuous and chopped fibers) such as asbestos,carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, or NEglasses, or the like; sulfides such as molybdenum sulfide, zinc sulfideor the like; barium compounds such as barium titanate, barium ferrite,barium sulfate, heavy spar, or the like; metals and metal oxides such asparticulate or fibrous aluminum, bronze, zinc, copper and nickel or thelike; flaked fillers such as glass flakes, flaked silicon carbide,aluminum diboride, aluminum flakes, steel flakes or the like; fibrousfillers, for example short inorganic fibers such as those derived fromblends comprising at least one of aluminum silicates, aluminum oxides,magnesium oxides, and calcium sulfate hemihydrate or the like; naturalfillers and reinforcements, such as wood flour obtained by pulverizingwood, fibrous products such as cellulose, cotton, sisal, jute, starch,cork flour, lignin, ground nut shells, corn, rice grain husks or thelike; organic fillers such as polytetrafluoroethylene; reinforcingorganic fibrous fillers formed from organic polymers capable of formingfibers such as poly(ether ketone), polyimide, polybenzoxazole,poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides,aromatic polyamides, polyetherimides, polytetrafluoroethylene, acrylicresins, poly(vinyl alcohol) or the like; as well as additional fillersand reinforcing agents such as mica, clay, feldspar, flue dust, fillite,quartz, quartzite, perlite, tripoli, diatomaceous earth, carbon black,or the like, or combinations comprising at least one of the foregoingfillers or reinforcing agents.

In some embodiments, the disclosed blended thermoplastic compositionscomprise a glass fiber component. In a further aspect, the glass fiberused is selected from E-glass, S-glass, AR-glass, T-glass. D-glass andR-glass. In a still further aspect, the glass fiber used is selectedfrom E-glass. S-glass, and combinations thereof. In a still furtheraspect, the glass fiber is one or more E-glass materials.

The glass fibers can be sized or unsized. Sized glass fibers are coatedon their surfaces with a sizing composition selected for compatibilitywith the polycarbonate. The sizing composition facilitates wet-out andwet-through of the polycarbonate upon the fiber strands and assists inattaining desired physical properties in the polycarbonate composition.

In various further aspects, the glass fiber is sized with a coatingagent. In a further aspect, the coating agent is present in an amountfrom 0.1 to 5 wt % based on the weight of the glass fibers. In a stillfurther aspect, the coating agent is present in an amount from 0.1 to 2wt % based on the weight of the glass fibers.

In preparing the glass fibers, a number of filaments can be formedsimultaneously, sized with the coating agent and then bundled into whatis called a strand. Alternatively the strand itself can be first formedof filaments and then sized. The amount of sizing employed is generallythat amount which is sufficient to bind the glass filaments into acontinuous strand and ranges from 0.1 to 5 wt %, 0.1 to 2 wt % based onthe weight of the glass fibers. Generally, this can be 1.0 wt % based onthe weight of the glass filament.

In a further aspect, the glass fiber can be continuous or chopped. In astill further aspect, the glass fiber is continuous. In yet a furtheraspect, the glass fiber is chopped. Glass fibers in the form of choppedstrands can have a length of 0.3 millimeters (mm) to 10 centimeters,specifically 0.5 millimeters to 5 centimeters, and more specifically 1.0millimeter to 2.5 centimeters. In various further aspects, the glassfiber has a length from 0.2 mm to 20 mm. In a yet further aspect, theglass fiber has a length from 0.2 mm to 10 mm. In an even furtheraspect, the glass fiber has a length from 0.7 mm to 7 mm. In this area,where a thermoplastic resin is reinforced with glass fibers in acomposite form, fibers having a length of 0.4 mm are generally referredto as long fibers, and shorter ones are referred to as short fibers. Ina still further aspect, the glass fiber can have a length of 1 mm orlonger. In yet a further aspect, the glass fiber can have a length of 2mm or longer.

In various further aspects, the glass fiber has a round (or circular),flat, or irregular cross-section. Thus, use of non-round fiber crosssections is possible. In a still further aspect, the glass fiber has acircular cross-section. In yet further aspect, the diameter of the glassfiber is from 1 to 15 micrometers (μm). In an even further aspect, thediameter of the glass fiber is from 4 to 10 μm. In a still furtheraspect, the diameter of the glass fiber is from 1 to 10 μm. In a stillfurther aspect, the glass fiber has a diameter from 7 μm to 10 μm.

The glass fiber component can be present in the composition in an amountfrom 5 to 40 wt %, 5 to 35 wt %, 10 to 30 wt %, 5 to 30 wt %, 5 to 20 wt%, 5 to 15%, or 10 to 20 wt %.

The composition can comprise anti-drip agents. The anti-drip agent canbe a fibril forming fluoropolymer such as polytetrafluoroethylene(PTFE). The anti-drip agent can be encapsulated by a rigid copolymer asdescribed above, for example styrene-acrylonitrile copolymer (SAN). PTFEencapsulated in SAN is known as TSAN. Encapsulated fluoropolymers can bemade by polymerizing the encapsulating polymer in the presence of thefluoropolymer, for example an aqueous dispersion. TSAN can providesignificant advantages over PTFE, in that TSAN can be more readilydispersed in the composition. An exemplary TSAN can comprise 50 wt %PTFE and 50 wt % SAN, based on the total weight of the encapsulatedfluoropolymer. The SAN can comprise, for example, 75 wt % styrene and 25wt % acrylonitrile based on the total weight of the copolymer.Alternatively, the fluoropolymer can be pre-blended in some manner witha second polymer, such as for, example, an aromatic polycarbonate or SANto form an agglomerated material for use as an anti-drip agent. Eithermethod can be used to produce an encapsulated fluoropolymer. Antidripagents are generally used in amounts of 0.1 to 5 wt %, based on 100parts by weight of the polymer component of the blend composition.

In certain embodiments, the anti-drip agent is TSAN. The TSAN can bepresent in an amount of 0.1 to 2.0 wt %, 0.1 to 1.0 wt %, 0.3 to 1.0 wt%, 0.3 to 0.7 wt %, 0.4 to 0.7 wt %, or 0.5 to 0.7 wt %, based on 100parts by weight of the polymer component of the blend composition. Incertain embodiments, the TSAN can be present in an amount of 0.3 wt %,0.4 wt %, 0.5 wt %, 0.6 wt %, or 0.7 wt %, based on 100 parts by weightof the polymer component of the blend composition.

The blend compositions can have a combination of desired properties. Thecompositions can have improved mechanical, thermal, or rheologicalproperties, or a combination thereof. The compositions can have improvedoptical properties. The compositions can have improved melt flow andheat resistance. The compositions can have improved melt flow, heatresistance, ductility, or impact resistance. The compositions can haveimproved flame retardance. Melt flow can be evaluated by, for example,melt viscosity, melt volume flow rate, or melt flow rate. Heatresistance can be evaluated by, for example. Tg, heat deformationtemperature, or Vicat softening temperature. Ductility and impactresistance can be evaluated by, for example, multi axial impact, andnotched Izod impact.

The blend compositions can be particularly suitable for use in themanufacture of metallized articles. An article can be molded from theblend composition and subsequently metallized. The metallized articlecan have a combination of desired properties. For example, themetallized article can have a desirable minimum haze onset value, metaladhesion, corrosion resistance, or combination thereof.

Melt viscosity (MV) of the blend compositions can be determined usingISO 11443 or ASTM D3835. Melt viscosity is a measurement of therheological characteristics of a composition at temperatures and shearconditions common to processing equipment. A lower value for meltviscosity indicates that the composition flows easier. Melt viscositycan be determined at different temperatures (e.g., 260° C., 280° C.,300° C., 316° C., or 330° C.) and different shear rates (e.g., 1500 or5000 second⁻¹). Melt viscosities are typically determined by pressing amolten composition through a die while measuring the pressure drop overthe complete or part of the die. Melt viscosities can be measured by,for example, a Kayeness Capillary viscometer (e.g., with a capillarylength:diameter ratio of 20:1, a capillary diameter of 1.0 millimeter, acapillary entrance angle of 180 degrees, and a dwell time of 4 minutes).Melt viscosity can be reported in Pascal-seconds (Pa-s) and the shearrate can be reported in reciprocal seconds. A melt viscosity measured ata shear rate of 5000 s⁻¹ can be referred to as a high shear meltviscosity value.

The blend compositions can have a melt viscosity of 50 to 400 MPa, 50 to375 MPa, 50 to 350 MPa, 50 to 325 MPa, 50 to 300 MPa, 50 to 275 MPa, 50to 250 MPa, 50 to 225 MPa, 50 to 200 MPa, 50 to 175 MPa, 50 to 150 MPa,100 to 375 MPa, 100 to 350 MPa, 100 to 325 MPa, 100 to 300 MPa, 100 to275 MPa, 100 to 250 MPa, 100 to 225 MPa, or 100 to 200 MPa, measured inaccordance with ISO 11443 at 300° C. at a shear rate of 1500 s⁻¹, ormeasured in accordance with ISO 11443 at 316° C. at a shear rate of 5000s⁻¹. The blend compositions can have a melt viscosity of less than orequal to 395 MPa, less than or equal to 390 MPa, less than or equal to385 MPa, less than or equal to 380 MPa, less than or equal to 375 MPa,less than or equal to 370 MPa, less than or equal to 365 MPa, less thanor equal to 360 MPa, less than or equal to 355 MPa, less than or equalto 350 MPa, less than or equal to 345 MPa, less than or equal to 340MPa, less than or equal to 335 MPa, less than or equal to 330 MPa, lessthan or equal to 325 MPa, less than or equal to 320 MPa, less than orequal to 315 MPa, less than or equal to 310 MPa, less than or equal to305 MPa, less than or equal to 300 MPa, less than or equal to 295 MPa,less than or equal to 290 MPa, less than or equal to 285 MPa, less thanor equal to 280 MPa, less than or equal to 275 MPa, less than or equalto 270 MPa, less than or equal to 265 MPa, less than or equal to 260MPa, less than or equal to 255 MPa, less than or equal to 250 MPa, lessthan or equal to 245 MPa, less than or equal to 240 MPa, less than orequal to 235 MPa, less than or equal to 230 MPa, less than or equal to225 MPa, less than or equal to 220 MPa, less than or equal to 215 MPa,less than or equal to 210 MPa, less than or equal to 205 MPa, less thanor equal to 200 MPa, less than or equal to 195 MPa, less than or equalto 190 MPa, less than or equal to 185 MPa, less than or equal to 180MPa, less than or equal to 175 MPa, less than or equal to 170 MPa, lessthan or equal to 165 MPa, less than or equal to 160 MPa, less than orequal to 155 MPa, less than or equal to 150 MPa, less than or equal to145 MPa, less than or equal to 140 MPa, less than or equal to 135 MPa,less than or equal to 130 MPa, less than or equal to 125 MPa, less thanor equal to 120 MPa, less than or equal to 115 MPa, less than or equalto 110 MPa, less than or equal to 105 MPa, less than or equal to 100MPa, less than or equal to 95 MPa, less than or equal to 90 MPa, lessthan or equal to 85 MPa, less than or equal to 80 MPa, less than orequal to 75 MPa, less than or equal to 70 MPa, less than or equal to 65MPa, less than or equal to 60 MPa, less than or equal to 55 MPa, or lessthan or equal to 50 MPa, measured in accordance with ISO 11443 at 300°C. at a shear rate of 1500 s⁻¹, or measured in accordance with ISO 11443at 316° C. at a shear rate of 5000 s⁻¹.

Melt volume flow rate (MVR) of the blend compositions can be determinedusing ISO 1133 or ASTM D1238. MVR measures the volume of a compositionextruded through an orifice at a prescribed temperature and load over aprescribed time period. The higher the MVR value of a polymercomposition at a specific temperature, the greater the flow of thatcomposition at that specific temperature.

MVR can be measured, for example, by packing a small amount of polymercomposition into an extruder barrel of an extruder. The composition canbe preheated for a specified amount of time at a particular temperature(the test temperature is usually set at or slightly above the meltingregion of the material being characterized). After preheating thecomposition, a particular weight (e.g., a 2.16 kg weight) can beintroduced to a piston, which acts as the medium that causes extrusionof the molten polymer composition. The weight exerts a force on thepiston and thereby the molten polymer composition, and the moltencomposition flows through the dye wherein the displacement of the moltencomposition is measured in cubic centimeters per over time such as 10minutes (cm³/10 min).

The compositions can have a MVR of 2 to 300 cm³/10 min. 2 to 200 cm³/10min, 2 to 100 cm³/10 min, 10 to 300 cm³/10 min. 20 to 300 cm³/10 min, 30to 300 cm³/10 min. 40 to 300 cm³/10 min, 50 to 300 cm³/10 min, 60 to 300cm³/10 min. 70 to 300 cm³/10 min, 80 to 300 cm³/10 min, 90 to 300 cm³/10min, 100 to 300 cm³/10 min, 50 to 200 cm³/10 min, 75 to 175 cm³/10 min,or 100 to 150 cm³/10 min, using the ISO 1133 method, 2.16 kg load, 330°C. temperature, 360 second dwell. The compositions can have a MVR of 5cm³/10 min or greater, 10 cm³/10 min or greater, 20 cm³/10 min orgreater, 30 cm³/10 min or greater, 40 cm³/10 min or greater, 50 cm³/10min or greater, 60 cm³/10 min or greater, 70 cm³/10 min or greater, 80cm³/10 min or greater, 90 cm³/10 min or greater, 100 cm³/10 min orgreater, 110 cm³/10 min or greater, 120 cm³/10 min or greater, 130cm³/10 min or greater, 140 cm³/10 min or greater, 150 cm³/10 min orgreater, 160 cm³/10 min or greater, 170 cm³/10 min or greater, 180cm³/10 min or greater, 190 cm³/10 min or greater, 200 cm³/1) min orgreater, 210 cm³/10 min or greater, 220 cm³/10 min or greater, 230cm³/10 min or greater, 240 cm³/10 min or greater, 250 cm³/10 min orgreater, 260 cm³/10 min or greater, 270 cm³/10 min or greater, 280cm³/10 min or greater, 290 cm³/10 min or greater, or 300 cm³/10 min orgreater, using the ISO 1133 method, 2.16 kg load, 330° C. temperature,360 second dwell.

the Tg of the blended compositions can be determined using DSC, forexample, with a heating rate of 10° C./minute and using the secondheating curve for Tg determination.

The blend compositions can have a Tg of greater than or equal to 120°C., greater than or equal to 125° C., greater than or equal to 130° C.,greater than or equal to 135° C., greater than or equal to 140° C.,greater than or equal to 145° C., greater than or equal to 150° C.,greater than or equal to 155° C., greater than or equal to 160° C.,greater than or equal to 165° C., greater than or equal to 170° C.,greater than or equal to 175° C., greater than or equal to 180° C.,greater than or equal to 185° C., greater than or equal to 190° C.,greater than or equal to 200° C., greater than or equal to 210° C.,greater than or equal to 220° C., greater than or equal to 230° C.,greater than or equal to 240° C., greater than or equal to 250° C.,greater than or equal to 260° C., greater than or equal to 270° C.,greater than or equal to 280° C., greater than or equal to 290° C., orgreater than or equal to 300° C., as measured using a differentialscanning calorimetry method. The compositions can have Tgs ranging from120 to 230° C., 140 to 185° C., 145 to 18° C., 150 to 175° C., 155 to170° C., or 160 to 165° C. The compositions can have a Tg of 150° C.,151° C., 152° C., 153° C., 154° C., 155° C., 156° C., 157° C., 158° C.,159° C., 160° C., 161° C., 162° C., 163° C., 164° C., 165° C., 166° C.,167° C., 168° C., 169° C., 170° C., 171° C., 172° C., 173° C., 174° C.,or 175° C.

Heat deflection temperature or heat distortion temperature (HDT) of theblended compositions can be determined according to ISO 75 or ASTM D648.HDT is a measure of heat resistance and is an indicator of the abilityof a material to withstand deformation from heat over time. A higheriHDT value indicates better heat resistance. Measurements can beperformed on molded ISO bars (80×10×4 mm) preconditioned at 23° C. and50% relative humidity for 48 hrs. The heating medium of the HDTequipment can be mineral oil. Measurements can be performed in duplicateand the average value reported.

The blend compositions can have an HDT of greater than or equal to 120°C., greater than or equal to 125° C., greater than or equal to 130° C.,greater than or equal to 135° C., greater than or equal to 140° C.,greater than or equal to 145° C., greater than or equal to 1500° C.,greater than or equal to 155° C., greater than or equal to 160° C.,greater than or equal to 165° C., greater than or equal to 170° C.,greater than or equal to 175° C., greater than or equal to 180° C.,greater than or equal to 185° C., greater than or equal to 190° C.,greater than or equal to 200° C., greater than or equal to 210° C.,greater than or equal to 220° C., greater than or equal to 230° C.,greater than or equal to 240° C., greater than or equal to 250° C.,greater than or equal to 260° C., greater than or equal to 270° C.,greater than or equal to 280° C., greater than or equal to 290° C., orgreater than or equal to 300° C., measured at 0.45 MPa stress or 1.8 MPastress in accordance with ISO 75. The compositions can have heatdeflection temperatures ranging from 120 to 230° C., 140 to 185° C., 145to 180° C., 150 to 175° C., 155 to 17° C., or 160 to 165° C., measuredat 0.45 MPa stress or 1.8 MPa stress in accordance with ISO 75. Thecompositions can have a heat deflection temperature of 150° C., 151° C.,152° C., 153° C., 154° C., 155° C., 156° C., 157° C., 158° C., 159° C.,160° C., 161° C., 162° C., 163° C., 164° C., 165° C., 166° C., 167° C.,168° C., 169° C., 170° C., 171° C., 172° C., 173° C., 174° C., or 175°C., measured at 0.45 MPa stress or 1.8 MPa stress in accordance with ISO75.

Multiaxial impact testing (MAI) can be performed according to ISO 6603or ASTM D3763. This procedure provides information on how a materialbehaves under multiaxial deformation conditions. The multiaxial impactvalue indicates the amount of energy the material absorbs during thetest; a higher value generally indicates a better result. Impactproperties that can be reported include Energy to Maximum Load. Energyto Failure, and Average Total Energy, all expressed in units of Joules.Ductility of tested parts can be expressed in percent (% D) based onwhether the part fractured in a brittle or ductile manner.

Multiaxial impact can be measured using injection molded plaques (e.g.,disks 3.2 mm thick and 10 centimeters in diameter). The plaques can beprepared using standard molding conditions or abusive moldingconditions. Standard molding conditions can refer to a barreltemperature of 580° F. and a residence time of 35 seconds. Abusivemolding conditions can refer to a barrel temperature of 580-620° F. anda residence time of 120 seconds. Abusive molding conditions can refer toconditions where the composition dwells in the molder barrel for anextended period of time and under elevated molding temperatures that cancause thermal degradation of one or more polymers in the composition. Anapparatus, such as a Dynatup, can be used to evaluate multiaxial impact,and can have a tup of 10 mm, 12.5 mm, or 20 mm. The impact velocity canbe 4.4 m/s. Measurements can be conducted at various temperatures (e.g.,23° C., 0° C., −30° C.).

The blend compositions can have an Energy to Maximum Load of 10 to 250Joules (J), 50 to 200 J, or 100 to 150 J, at 23° C., 0° C., or −30° C.,molded under standard molding conditions. The blend compositions canhave an Energy to Maximum Load of greater than or equal to 10 J, greaterthan or equal to 25 J, greater than or equal to 50 J, greater than orequal to 75 J, greater than or equal to 100 J, greater than or equal to125 J, greater than or equal to 150 J, greater than or equal to 175 J,or greater than or equal to 200 J, at 23° C., 0° C., or −30° C., moldedunder standard molding conditions.

The blend compositions can have an Energy to Maximum Load of 10 to 250J, 50 to 200 J, or 100 to 150 J, at 23° C., 0° C., or −30° C., moldedunder abusive molding conditions. The blend compositions can have anEnergy to Maximum Load of greater than or equal to 10 J, greater than orequal to 25 J, greater than or equal to 50 J, greater than or equal to75 J, greater than or equal to 100 J, greater than or equal to 125 J,greater than or equal to 150 J, greater than or equal to 175 J, orgreater than or equal to 200 J, at 23° C., 0° C., or −30° C., moldedunder abusive molding conditions.

The blend compositions can have an Energy to Failure of 10 J to 250 J,50 J to 200 J, or 100 J to 150 J, at 23° C., 0° C., or −30° C., moldedunder standard molding conditions. The blend compositions can have anEnergy to Failure of greater than or equal to 10 J, greater than orequal to 25 J, greater than or equal to 50 J, greater than or equal to75 J, greater than or equal to 100 J, greater than or equal to 125 J,greater than or equal to 150 J, greater than or equal to 175 J, orgreater than or equal to 200 J, at 23° C., 0° C., or −30° C., moldedunder standard molding conditions.

The blend compositions can have an Energy to Failure of 10 J to 250 J,50 J to 200 J, or 100 J to 150 J, at 23° C., 0° C., or −30° C., moldedunder abusive molding conditions. The blend compositions can have anEnergy to Failure of greater than or equal to 10 J, greater than orequal to 25 J, greater than or equal to 50 J, greater than or equal to75 J, greater than or equal to 100 J, greater than or equal to 125 J,greater than or equal to 150 J, greater than or equal to 175 J, orgreater than or equal to 200 J, at 23° C., 0° C., or −30° C., moldedunder abusive molding conditions.

The blend compositions can have an Average Total Energy of 10 to 250 J,50 to 200 J, or 100 to 150 J, at 23° C., 0° C., or −30° C., molded understandard molding conditions. The blend compositions can have an AverageTotal Energy of greater than or equal to 10 J, greater than or equal to25 J, greater than or equal to 50 J, greater than or equal to 75 J,greater than or equal to 100 J, greater than or equal to 125 J, greaterthan or equal to 150 J, greater than or equal to 175 J, or greater thanor equal to 200 J, at 23° C., 0° C., or −30° C., molded under standardmolding conditions.

The blend compositions can have an Average Total Energy of 10 to 250 J,50 to 200 J, or 100 to 150 J, at 23° C., 0° C., or −30° C., molded underabusive molding conditions. The blend compositions can have an AverageTotal Energy of greater than or equal to 10 J, greater than or equal to25 J, greater than or equal to 50 J, greater than or equal to 75 J,greater than or equal to 100 J, greater than or equal to 125 J, greaterthan or equal to 150 J, greater than or equal to 175 J, or greater thanor equal to 200 J, at 23° C., 0° C., or −30° C., molded under abusivemolding conditions.

The blend compositions can possess a ductility of greater than or equalto 50%, greater than or equal to 55%, greater than or equal to 60%,greater than or equal to 65%, greater than or equal to 70%, greater thanor equal to 75%, greater than or equal to 80%, greater than or equal to85%, greater than or equal to 90%, greater than or equal to 95%, or 100%in a multiaxial impact test at 23° C., 0° C., or −30° C., molded understandard molding conditions.

The blend compositions can possess a ductility of greater than or equalto 50%, greater than or equal to 55%, greater than or equal to 60%,greater than or equal to 65%, greater than or equal to 70%, greater thanor equal to 75%, greater than or equal to 80%, greater than or equal to85%, greater than or equal to 90%, greater than or equal to 95%, or 100%in a multiaxial impact test at 23° C., 0° C., or −30° C., molded underabusive molding conditions.

The blend compositions can have a notched izod impact energy (NII). Ahigher NII value indicates better impact strength. The polycarbonatecompositions can have a notched izod impact energy (NII) of greater thanor equal to 4 Joules per meter (J/m), greater than or equal to 5 J/m,greater than or equal to 6 J/m, greater than or equal to 7 J/m, greaterthan or equal to 8 J/m, greater than or equal to 9 J/m, greater than orequal to 10 J/m, greater than or equal to 11 J/m, greater than or equalto 12 J/m, greater than or equal to 13 J/m, greater than or equal to 14J/m, greater than or equal to 15 J/m, greater than or equal to 16 J/m,greater than or equal to 17 J/m, greater than or equal to 18 J/m,greater than or equal to 19 J/m, greater than or equal to 20 J/m,greater than or equal to 21 J/m, greater than or equal to 22 Jim,greater than or equal to 23 J/m, greater than or equal to 24 J/m,greater than or equal to 25 J/m, greater than or equal to 26 J/m,greater than or equal to 27 J/m, greater than or equal to 28 J/m,greater than or equal to 29 J/m, greater than or equal to 30 J/m,greater than or equal to 31 J/m, greater than or equal to 32 J/m,greater than or equal to 33 J/m, greater than or equal to 34 J/m,greater than or equal to 35 J/m, greater than or equal to 36 J/m,greater than or equal to 37 J/m, greater than or equal to 38 J/m,greater than or equal to 39 J/m, greater than or equal to 40 J/m,greater than or equal to 41 J/m, greater than or equal to 42 J/m,greater than or equal to 43 J/m, greater than or equal to 44 J/m,greater than or equal to 45 J/m, greater than or equal to 46 J/m,greater than or equal to 47 J/nm greater than or equal to 48 J/m,greater than or equal to 49 J/m, greater than or equal to 50 J/m,greater than or equal to 51 J/m, greater than or equal to 52 J/m,greater than or equal to 53 J/m, greater than or equal to 54 J/m,greater than or equal to 55 J/m, greater than or equal to 56 J/m,greater than or equal to 57 J/m, greater than or equal to 58 J/m,greater than or equal to 59 J/m, or greater than or equal to 60 J/m,measured at 23° C., 0° C., or −30° C. according to ASTM D 256.

The blend compositions can possess a ductility of greater than or equalto 50%, greater than or equal to 55%, greater than or equal to 60%,greater than or equal to 65%, greater than or equal to 70%, greater thanor equal to 75%, greater than or equal to 80%, greater than or equal to85%, greater than or equal to 90%, greater than or equal to 95%, or 100%in a notched izod impact test at −20° C., −15° C., −10° C., 0° C., 5°C., 10° C., 15° C., 20° C., 23° C., 25° C., 30° C., or 35° C. at athickness of 3.2 mm according to ASTM D 256.

Flammability tests can be performed following the procedure ofUnderwriter's Laboratory Bulletin 94 entitled “Tests for Flammability ofPlastic Materials, UL94.” According to this procedure, materials can beclassified as V-0, V-1 or V-2 on the basis of the test results obtainedfor samples of 1.5 to 2.0 millimeter thickness. The samples are madeaccording to the UL94 test procedure using standard ASTM moldingcriteria. The criteria for each of the flammability classificationstested are described below.

V0: In a sample placed so that its long axis is 180 degrees to theflame, the average period of flaming and smoldering after removing theigniting flame does not exceed five seconds and none of the verticallyplaced samples produces drips of burning particles that ignite absorbentcotton, and no specimen burns up to the holding clamp after flame orafter glow. Five bars flame out time (FOT) is the sum of the flame outtime for five bars each lit twice for ten (10) seconds each, for amaximum flame out time of 50 seconds. FOT1 is the average flame out timeafter the first light. FOT2 is the average flame out time after thesecond light.

V-1, V-2: In a sample placed so that its long axis is 180 degrees to theflame, the average period of flaming and smoldering after removing theigniting flame does not exceed twenty-five seconds and, for a V-1rating, none of the vertically placed samples produces drips of burningparticles that ignite absorbent cotton. The V2 standard is the same asV-1, except that flaming drips that ignite the cotton are permitted.Five bar flame out time (FOT) is the sum of the flame out time for fivebars, each lit twice for ten (10) seconds each, for a maximum flame outtime of 250 seconds.

The data can also be analyzed by calculating the average flame out time,standard deviation of the flame out time and the total number of drips,and by using statistical methods to convert that data to a prediction ofthe probability of first time pass, or “p(FTP)”, that a particularsample formulation would achieve a “pass” rating in the conventionalUL94 V0 or V1 testing of 5 bars. The probability of a first time pass ona first submission (pFTP) can be determined according to the formula:

PFTP=(P _(t1>mbt,n=0) ×P _(t2>mbt,n=0) ×P _(total<=mtbt) ×P _(drip,n=0))

where P_(t1>mbt, n=0) is the probability that no first burn time exceedsa maximum burn time value, P_(t2>mbt, n=0) is the probability that nosecond burn time exceeds a maximum burn time value, P_(total<=mtbt) isthe probability that the sum of the burn times is less than or equal toa maximum total burn time value, and P_(drip, n=0) is the probabilitythat no specimen exhibits dripping during the flame test. First andsecond burn time refer to burn times after a first and secondapplication of the flame, respectively.

The probability that no first burn time exceeds a maximum burn timevalue, P_(t1>mbt, n=0), can be determined from the formula:P_(t1>mbt, n=0)=(1−P_(t1>mbt))⁵ where P_(t1>mbt) is the area under thelog normal distribution curve for t1>mbt, and where the exponent “5”relates to the number of bars tested. The probability that no secondburn time exceeds a maximum burn time value can be determined from theformula: P_(t2>mbt, n=0)=(1−P_(t2>mbt)) where P_(t2>mbt) is the areaunder the normal distribution curve for t2>mbt. As above, the mean andstandard deviation of the burn time data set are used to calculate thenormal distribution curve. For the UL-94 V-0 rating, the maximum burntime is 10 seconds. For a V-1 or V-2 rating the maximum burn time is 30seconds. The probability P_(drip, n=0) that no specimen exhibitsdripping during the flame test is an attribute function, estimated by:(1−P_(drip))⁵ where P_(drip)=(the number of bars that drip/the number ofbars tested).

The probability P_(total<=mtbt) that the sum of the burn times is lessthan or equal to a maximum total burn time value can be determined froma normal distribution curve of simulated 5-bar total burn times. Thedistribution can be generated from a Monte Carlo simulation of 1000 setsof five bars using the distribution for the burn time data determinedabove. Techniques for Monte Carlo simulation are well known in the art.A normal distribution curve for 5-bar total burn times can be generatedusing the mean and standard deviation of the simulated 1000 sets.Therefore, P_(total<=mtbt) can be determined from the area under a lognormal distribution curve of a set of 1000 Monte Carlo simulated 5-bartotal burn time for total<=maximum total burn time. For the UL-94 V-0rating, the maximum total burn time is 50 seconds. For a V-1 or V-2rating, the maximum total burn time is 250 seconds.

Preferably, p(FTP) is as close to 1 as possible, for example, greaterthan or equal to 0.6, or greater than or equal to 0.7, or greater thanor equal to 0.8 or, more specifically, greater than or equal to 0.85,for maximum flame-retardant performance in UL testing. The p(FTP)>0.7,and specifically, p(FTP)>0.85, is a more stringent standard than merelyspecifying compliance with the referenced V-0 or V-1 test.

The compositions disclosed herein can be manufactured by variousmethods. For example, a composition can be first mixed in a high speedHENSCHEL-Mixer. Other low shear processes, including but not limited tohand mixing, can also accomplish this blending. The mixed compositioncan then be fed into the throat of a single or twin-screw extruder via ahopper. Alternatively, at least one of the components can beincorporated into the composition by feeding directly into the extruderat the throat or downstream through a side-stuffer. Additives can alsobe compounded into a master-batch with a desired polymeric resin and fedinto the extruder. The extruder can be generally operated at atemperature higher than that necessary to cause the composition to flow.The extrudate can be immediately quenched in a water batch andpelletized. The pellets, so prepared, when cutting the extrudate can beone-fourth inch long or less as desired. Such pellets can be used forsubsequent molding, shaping, or forming.

In certain embodiments, the compositions can undergo a reactiveextrusion process, as described herein, by injection of a redistributioncatalyst into the extruder during the extrusion process.

Shaped, formed, or molded articles comprising the polycarbonatecompositions are also provided. The article can be a metallized article.The article can be metallized with, for example, chrome, nickel, oraluminum. The article can optionally include an intervening base coatbetween the molded article and the metal.

Articles that can be prepared using the polycarbonate compositionsinclude, for example, automotive, aircraft, and watercraft exterior andinterior components. Exemplary articles include, but are not limited to,instrument panels, overhead consoles, interior trim, center consoles,panels, quarter panels, rocker panels, trim, fenders, doors, deck lids,trunk lids, hoods, bonnets, roofs, bumpers, fascia, grilles, minorhousings, pillar appliqués, cladding, body side moldings, wheel covers,hubcaps, door handles, spoilers, window frames, headlamp bezels,headlamps, tail lamps, tail lamp housings, tail lamp bezels, licenseplate enclosures, roof racks, circuit breakers, electrical andelectronic housings, and running boards, or any combination thereof. Incertain embodiments, the article is a metallized automotive bezel.

Exemplary articles include, for example, a medical device, a displaydevice, a projector lens, a heat shield, a lighting source enclosure, alighting source lens, a computer monitor screen, a laptop screen, aliquid crystal display screen, an organic light-emitting diode screen,computer and business machine housings (e.g., housings for monitors,handheld electronic device housings such as housings for cell phones),electrical connectors, components of lighting fixtures, ornaments, homeappliances, roofs, greenhouses, sun rooms, swimming pool enclosures,electronic device casings and signs and the like.

Exemplary articles include, for example, enclosures, housings, panels,and parts for outdoor vehicles and devices; enclosures for electricaland telecommunication devices; outdoor furniture; aircraft components;boats and marine equipment, including trim, enclosures, and housings;outboard motor housings; depth finder housings; personal water-craft;jet-skis; pools; spas; hot tubs; steps; step coverings; building andconstruction applications such as glazing, roofs, windows, floors,decorative window furnishings or treatments; treated glass covers forpictures, paintings, posters, and like display items; wall panels, anddoors; counter tops; protected graphics; outdoor and indoor signs;enclosures, housings, panels, and parts for automatic teller machines(ATM); computer; desk-top computer; portable computer; lap-top computer;hand held computer housings; monitor; printer; keyboards; FAX machine;copier; telephone; phone bezels; mobile phone; radio sender; radioreceiver; enclosures, housings, panels, and parts for lawn and gardentractors, lawn mowers, and tools, including lawn and garden tools;window and door trim; sports equipment and toys; enclosures, housings,panels, and parts for snowmobiles; recreational vehicle panels andcomponents; playground equipment; shoe laces; articles made fromplastic-wood combinations; golf course markers; utility pit covers;light fixtures; lighting appliances; network interface device housings;transformer housings; air conditioner housings; cladding or seating forpublic transportation; cladding or seating for trains, subways, orbuses; meter housings; antenna housings; cladding for satellite dishes;coated helmets and personal protective equipment; coated synthetic ornatural textiles; coated painted articles; coated dyed articles; coatedfluorescent articles; coated foam articles; and like applications.

The article can be an automotive bezel, an automobile headlamp lens(e.g., an outer headlamp lens or an inner headlamp lens), or a headlampassembly comprising: a headlamp lens; a headlamp reflector; a bezel; anda housing. The headlamp assembly can further comprise atungsten-halogen, a halogen infrared reflective, or a high-intensitydischarge light source.

In certain embodiments, an article molded from the thermoplasticcomposition (via, e.g., injection molding) has no surface defectsvisible to the eye on a surface thereof. In certain embodiments, when asurface of the molded article is metallized, the metallized surface hasno surface defects visible to the eye. A base coat can be presentbetween the article and the metallized surface, or the surface of thearticle can be directly metallized without a base coat.

In certain embodiments, a surface of an article molded from thethermoplastic composition (via, e.g., injection molding) exhibits agloss of greater than 95 units, measured at 20 degrees using a triglossmeter. In certain embodiments, when a surface of the molded article ismetallized, the metallized surface has a gloss of greater than 1000units, greater than 1100 units, greater than 1200 units, greater than1300 units, greater than 1400 units, greater than 1500 units, greaterthan 1600 units, or greater than 1700 units, measured at 20 degreesusing a trigloss meter. A base coat can be present between the articleand the metallized surface, or the surface of the article can bedirectly metallized without a base coat.

The gloss of the molded articles can be further heat stable. Forexample, there is provided an article formed from the compositions (via.e.g., injection molding), and having a metallized surface, wherein themetallized surface retains 80% or more, 85% or more, 90% or more, or 95%or more of its gloss after heat aging at 150° C. for 1 hour, measured at20 degrees using a trigloss meter. A base coat can be present betweenthe article and the metallized surface, or the surface of the articlecan be directly metallized without a base coat.

There is also provided an article formed from the compositions (via,e.g., injection molding), and having a metallized surface, wherein themetallized surface retains 80% or more, 85% or more, 90% or more, or 95%or more of its gloss after heat aging at 160° C. for 1 hour, measured at20 degrees using a trigloss meter. A base coat can be present betweenthe article and the metallized surface, or the surface of the articlecan be directly metallized without a base coat.

In certain embodiments, there is provided an article formed from thecompositions, specifically a composition having up to 2 wt % of aparticulate filler, or no filler, and having a metallized surface,wherein the metallized surface retains 80% or more, 85% or more, 90% ormore, or 95% or more of its gloss after heat aging at 150° C. for 1hour, measured at 20 degrees using a tri gloss meter. An undercoat canbe present between the article and the metallized surface, or a surfaceof the article can be directly metallized.

In certain embodiments, there is provided an article formed from thecompositions, where the compositions include one or more additives suchas, for example, antioxidants, flame retardants, heat stabilizers, lightstabilizers, antistatic agents, colorants, and the like. An antioxidantstabilizer composition can be used, such as for example a hindered diolstabilizer, a thioester stabilizer, an amine stabilizer, a phosphitestabilizer, or a combination comprising at least one of the foregoingtypes of stabilizers.

The polycarbonate compositions can be molded into useful shaped articlesby a variety of methods, such as injection molding, extrusion,rotational molding, compression molding, blow molding, sheet or filmextrusion, profile extrusion, gas assist molding, structural foammolding, and thermoforming. Additional fabrication operations forpreparing the articles include, but are not limited to, molding, in-molddecoration, baking in a paint oven, lamination, metallization, andthermoforming.

Various types of gates can be employed for preparing molded articles,such as for example, side gates, spoke gates, pin gates, submarinegates, film gates, disk gates, or any combination thereof.Considerations in gating include part design, flow, end userequirements, and location of in-mold graphics. The standard guidelinesof traditional gating can apply, along with several extraconsiderations. For example, one gate can be used whenever possible tominimize the potential for wrinkling a film. Gates can be located awayfrom end-use impact as well as to provide flow from thick to thinsections to minimize weld lines. Gates can also be located at rightangles to a runner to minimize jetting, splay and gate blush. Largeparts requiring multiple gates can include gate positions close enoughtogether to reduce pressure loss. Sequential gating can be used toprevent folding of a film at weld lines. Gate land lengths can be keptas short as possible. An impinging gate can be used to ensure that theincoming flow is directed against the cavity wall or core to preventjetting. Venting (particularly full perimeter venting) can beaccomplished by knock outs, cores, and parting lines and can be usedwhenever possible to avoid trapped gas that can burn and rupture a film.In addition, flow restrictions near gate areas can increase thepotential for wash out due to increased shear. If bosses, core shutoffs,etc., are needed near a gate, rounded features or corners can be used toreduce shear. Gating for distributing injection pressure over a largearea, thus reducing the shear forces at the gate, include fan gates andsubmarine gates that enter the part via a rib. It is common to add apuddle or thicker area at a gate entrance point for gates like valvegates, hot drops, and cashew gates.

The article can be produced by a manufacturing process. The process caninclude (a) providing a polycarbonate composition as disclosed herein;(b) melting the composition, for example at 200-400° C., 225-350° C., or270-300° C. in an extruder; (c) extruding the composition; and (d)isolating the composition. The article can be further produced by (e)drying the composition and (1) melt forming the composition.

A method of preparing a metallized article can include molding acomposition into a predetermined mold dimensioned to a selected articleas described above; and subjecting the molded article to a metallizationprocess (e.g., vacuum deposition processes, vacuum sputtering processes,or a combination thereof). An exemplary method can include the generalsteps of an initial pump down on a molded article in a vacuum chamber;glow discharge/plasma clear; and metal deposition and application of atopcoat. Exemplary metals for metallization include, but are not limitedto, chrome, nickel, and aluminum. The surface of the molded item can becleaned and degreased before vapor deposition in order to increaseadhesion. A base coat can optionally be applied before metallization,for example, to improve metal layer adhesion. In certain embodiments,the metallized article is manufactured without applying a base coatprior to metallization.

A method of preparing a metallized article can include molding anarticle and subsequently metallizing the article using a physical vapordeposition (PVI) metallization process. During the metallizationprocess, high vacuum can be applied and the article treated with plasmato create a polar surface to enhance adhesion. Subsequent to plasmatreatment, a metal (e.g., aluminum) can be vaporized to deposit aselected thickness (e.g., 100 nm to 150 nm) of metal layer onto thearticle surface. This step can be followed with applying aplasma-deposit siloxane hardcoat of selected thickness (e.g., 50 nm) toprotect the metal layer against oxidation and scratches.

A method of preparing a metallized article can include mounting anarticle (e.g., on a rack) after molding and cleaning the article (e.g.,with ionized air); positioning the article in a vacuum chamber; andmetallizing the article under reduced pressure (e.g., using physicalvapor deposition). After metallization, a protective transparent layercan be applied to the metallized article. For example,hexamethyldisiloxane (HMDS) or SiOx can be applied in the vacuumchamber, or a silicone hard coat can be applied outside the vacuumchamber. In certain embodiments, the metallization process includes thesteps of forepumping, glow discharge, high vacuum pumping, coating(thermal coating in high vacuum), cool-down time, protective coating(glow discharge polymerization), venting, and charging.

A method of preparing a metallized article can include drying a moldedarticle (e.g., in a circulating oven) at a selected temperature (e.g.,275° F.) and time (e.g., 8 hours). The molded article can optionally beplaced in a bag (e.g., ziplock bag) and heat sealed to minimize moistureuptake prior to metallization. The molded article can be placed on anopen rack in a controlled environment at a selected temperature (e.g.,23° C.), and humidity (e.g., 50% relative humidity), and for a selectedtime (e.g., 1 to 5 days). The molded article can then be metallized(e.g., with evaporative metallization or sputtering). Evaporativemetallization can include the process of having a metal resistivelyheated under deep vacuum that is subsequently allowed to cool ontoexposed surfaces.

A method of preparing a metallized article can include providing anarticle into a vacuum chamber and pumping down the vacuum chamber (e.g.,using a roughing pump to obtain a pressure of 8×10⁻² mbar, following bya fine pump to achieve a pressure of 1×10⁻³ mbar). After the pump down,the pressure can be increased (e.g., to 2.5×10⁻² mbar) by adding aselected gas (e.g., argon or an oxygen/argon mixture) into the chamber.A glow discharge plasma clean can be implemented (e.g., at 40 kHz/3 kW)to prepare the article surface for metallization. The chamber can thenbe pumped down to a suitable pressure (e.g., 1.3×10⁻⁴) prior tometallization. Next, metal deposition (e.g., aluminum deposition) can beimplemented for a suitable time (e.g., 1 minute) to apply a selectedthickness of metal (e.g., 70 to 100 nm). Following evaporativedeposition of the metal, the pressure can be increased in the vacuumchamber (e.g., to 4×10⁻² mbar) in preparation for topcoat application(e.g., HMDS topcoat). The topcoat material (e.g., HDMS) can beintroduced into the vacuum chamber to apply a protective layer (e.g., a45 nm protective HMDS layer) under glow discharge conditions (e.g., for180 min).

A method of preparing a metallized article can include an initial pumpdown (e.g., less than 10⁻⁵ Mbar); glow discharge pretreatment (e.g.,using air, pressure of 10⁻¹ Mbar, voltage 4 Kv, time 1 minute); pumpdown (e.g., less than 10⁻⁵ Mbar); thermal aluminum evaporation (e.g., in1 minute); and plasil protective layer application under glow discharge(e.g., using air, pressure 10⁻¹ Mbar, voltage 4Kv, time 1 minute).

A method of preparing a metallized article can provide an article with ametal layer thickness of, for example, 10 to 300 nanometers (nm), 50 to200 nm, 75 to 175 nm, 100 to 150 nm, or 70 to 100 nm. The thickness ofthe metal layer (e.g., an aluminum layer) can be 50 nm, 55 nm, 60 nm, 65nm, 70 nm, 75 nm, 80 nm, 90 nm, 95 nm, 100 nm, 105 nm, 110 nm, 115 nm,120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 150, 155 nm, 150, 155 nm, 160 nm165 nm, 170 nm, 175 nm, 180 nm, 185 nm, 190 nm, 195 nm, or 200 nm.

A topcoat (e.g., siloxane hard-coat) can be applied to a metallizedarticle, the topcoat having a thickness of, for example, 5 to 150 nm, 10to 100 nm, 30 to 75 nm, 40 to 60 nm, or 45 to 55 nm. The thickness ofthe topcoat can be 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95nm, or 100 nm.

A wide variety of articles can be manufactured using the disclosedcompositions, including components for lighting articles, particularlyoptical reflectors. The optical reflectors can be used in automotiveheadlamps, headlamp bezels, headlight extensions and headlampreflectors, for indoor illumination, for vehicle interior illumination,and the like.

In the manufacture of an optical reflector, the thermoplasticcomposition can be molded, an optional base coat can be applied to asurface of the article, followed by metallization of the surface. Incertain embodiments, a base coat is not applied to a surface of themolded article prior to metallization. The surfaces of the molded itemsare smooth and good gloss can be obtained even by direct metal vapordeposition without treating the molded item with primer. Moreover,because the release properties of the molded item during injectionmolding are good, the surface properties of the molded item are superiorwithout replication of mold unevenness.

The articles, in particular lighting articles, can have one or more ofthe following properties: very low mold shrinkage; good surface glosseven when metal layers are directly vapor deposited; no residue on themold after long molding runs; and the vapor deposited surfaces do notbecome cloudy or have rainbow patterns even on heating of the vapordeposited surface. The articles further can have good heat stability.

The polycarbonate blend compositions preferably have one or morebeneficial properties for the production of heat resistant articles(e.g., automotive bezels), and in particular, metallizable heatresistant articles. The polycarbonate blend compositions can exhibit acombination of desirable properties, and in particular, thermal,mechanical, and rheological properties. For example, the polycarbonateblend compositions can exhibit a combination of one or more of heatresistance, impact resistance, low temperature ductility, low meltviscosity, good melt stability, and low mold stress. The compositionscan be used for the production of articles, including thin-walledarticles, having superior thermal and mechanical performance compared tocurrently available technologies. The compositions can be particularlysuitable for use in preparing metallized articles, and in particular,metallized articles exhibiting desirable haze onset temperatures, goodmetal adhesion to the article, and high corrosion resistance.

The polycarbonate blend compositions can include one or more componentsconfigured to enhance one or more of the thermal, mechanical,rheological, and metallization performance of the blend compositions. Ithas been unexpectedly found that the compositions disclosed herein canbe prepared having a combination of flame retardant, thermal,mechanical, and rheological properties that exceed currently availabletechnologies. In addition, the compositions can be used to preparemetallized articles to meet design demands.

The polycarbonate blend compositions can include one or more high heatpolycarbonates to enhance one or more of the thermal, mechanical,rheological, and metallization performance of the blend compositions.Exemplary high heat polycarbonates for inclusion in the blendcompositions include polycarbonates derived from2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP). Thepolycarbonate can be derived from PPPBP and Bisphenol A (BPA). ThePPPBP-BPA copolymer can be prepared by interfacial polymerization or bya melt process. The PPPBP-BPA copolymer can have endcaps derived fromparacumyl phenol (PCP), for example.

The PPPBP-BPA copolymer can include 1 to 50 mol % PPPBP, 10 to 45 mol %PPPBP, 15 to 40 nmol % PPPBP, 20 to 35 mol % PPPBP, 25 to 40 mol %PPPBP, 25 to 35 mol % PPPBP, 30 to 35 mol % PPPBP, or 32 to 33 mol %PPPBP. The PPPBP-BPA copolymer can include 1 mol %, 2 mol %, 3 mol %, 4mol %, 5 mol %, 6 mol %, 7 mol %, 8 mol %, 9 mol %, 10 mol %, 11 mol %,12 mol %, 13 mol %, 14 mol %, 15 mol %, 16 mol %, 17 mol %, 18 mol %, 19mol %, 20 mol %, 21 mol %, 22 mol %, 23 mol %, 24 mol %, 25 mol %, 26mol %, 27 mol %, 28 mol %, 29 mol %, 30 mol %, 31 mol %, 32 mol %, 33mol %, 34 mol %, 35 mol %, 36 mol %, 37 nmol %, 38 mol %, 39 mol %, 40mol %, 41 mol %, 42 mol %, 43 mol %, 44 mol %, 45 mol %, 46 mol %, 47nmol %, 48 mol %, 49 mol %, or 50 mol % PPPBP. The PPPBP-BPA copolymercan include 18 mol % PPPBP. The PPPBP-BPA copolymer can include 32 mol %PPPBP.

The PPPBP-BPA copolymer can have a weight average molecular weight of15,500 to 40,000 g/mol, 16,000 to 35,000 g/mol, 17,000 to 30,000 g/mol,15,500 to 25,000 g/mol, 15,500 to 23,000 g/mol, 17,000 to 23,000 g/mol,or 17,000 to 20.000 g/mol. The PPPBP-BPA copolymer, optionally havingparacumyl phenol derived endcaps, can have a weight average molecularweight of 15.500 g/mol, 16,000 g/mol, 16,500 g/mol, 17,000 g/mol, 17,500g/mol, 18,000 g/mol, 18,500 g/mol, 19,000 g/mol, 19,500 g/mol, 20,000g/mol, 20,500 g/mol, 21,000 g/mol, 21,500 g/mol, 22,000 g/mol, 22,500g/mol, 23,000 g/mol, 23,500 g/mol, 24,000 g/mol, 24,500 g/mol, 25,000g/mol, 25,500 g/mol, 26,000 g/mol, 26,500 g/mol, 27,000 g/mol, 27,500g/mol, 28,000 g/mol, 28,500 g/mol, 29,000 g/mol, 29,500 g/mol, or 30,000g/mol. The PPPBP-BPA copolymer can have a weight average molecularweight of 17,000 g/mol, 20,000 g/mol, or 23,000 g/mol. The PPPBP-BPAcopolymer can have a weight average molecular weight of 17,300 g/mol,19,900 g/mol, or 23,000 g/mol. Weight average molecular weight can bedetermined by GPC using BPA polycarbonate standards.

The PPPBP-BPA copolymers can have a polydispersity index (PDI) of 1.0 to10.0, 2.0 to 7.0, or 2.0 to 3.0. In certain embodiments, the PPPBP-BPAcopolymer have a PDI of 1.00, 1.50, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50,5.00, 5.50, 6.00, 6.50, 7.00, or 7.50. In certain embodiments, thePPPBP-BPA copolymers have a PDI of 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, 2.8, 2.9, or 3.0. In certain embodiments, the PPPBP-BPA copolymershave a PDI of 2.2 or 2.3.

The PPPBP-BPA copolymer can have a Tg of greater than or equal to 150°C., greater than or equal to 155° C., greater than or equal to 160° C.,greater than or equal to 165° C., greater than or equal to 170° C.,greater than or equal to 175° C., greater than or equal to 180° C.,greater than or equal to 185° C., greater than or equal to 190° C.,greater than or equal to 200° C., greater than or equal to 210° C.,greater than or equal to 220° C., greater than or equal to 230° C.,greater than or equal to 240° C., greater than or equal to 250° C.,greater than or equal to 260° C., greater than or equal to 270° C.,greater than or equal to 280° C., greater than or equal to 290° C., orgreater than or equal to 300° C., as measured using a differentialscanning calorimetry method.

The PPPBP-BPA copolymer can be present in the blend compositions in anamount ranging from 30 to 95 wt %, 35 to 95 wt %, 40 to 95 wt %, 45 to95 wt %, 50 to 95 wt %, 55 to 95 wt %, 60 to 95 wt %, 60 to 90 wt %, 60to 85 wt %, or 60 to 80 wt %, based on total weight of the composition.The PPPBP-BPA copolymer can be present in the blend compositions in anamount of 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45 wt %, 46 wt %,47 wt %, 48 wt %, 49 wt %, 50 wt %, 51 wt %, 52 wt %, 53 wt %, 54 wt %,55 wt %, 56 wt %, 57 wt %, 58 wt %, 59 wt %, 60 wt %, 61 wt %, 62 wt %,63 wt %, 64 wt %, 65 wt %, 66 wt %, 67 wt %, 68 wt %, 69 wt %, 70 wt %,71 wt %, 72 wt %, 73 wt %, 74 wt %, 75 wt %, 76 wt %, 77 wt %, 78 wt %,79 wt %, 80 wt %, 81 wt %, 82 wt %, 83 wt %, 84 wt %, 85 wt %, 86 wt %,87 wt %, 88 wt %, 89 wt %, or 90 wt %, based on total weight of thecomposition.

In certain embodiments, the blend compositions include a PPPBP-BPAcopolymer selected from the group consisting of: a PCP end-capped linearPPPBP-BPA copolymer having a weight average molecular weight of 23,000g/mol [^(±)1,000 g/mol]; a PCP end-capped linear PPPBP-BPA copolymerhaving a weight average molecular weight of 20,000 g/mol [^(±)1,000g/mol]; and a PCP end-capped linear PPPBP-BPA copolymer having a weightaverage molecular weight of 17,000 g/mol [^(±)1,000 g/mol]; or anycombination thereof; wherein the weight average molecular weight is asdetermined by GPC using BPA polycarbonate standards. In certainembodiments, the PPPBP-BPA copolymers include 31 to 35 mol % PPPBPcontent, or 32 to 33 mol % PPPBP content.

The polycarbonate blend compositions can include one or morepolycarbonates to enhance one or more of the thermal, mechanical,rheological, and metallization performance of the blend compositions.Exemplary polycarbonates for inclusion in the blend compositions includehomopolycarbonates derived from Bisphenol A. The BPA polycarbonate canbe prepared by interfacial polymerization or by a melt process. The BPApolycarbonate can have endcaps derived from phenol, paracumyl phenol(PCP), or a combination thereof.

The BPA polycarbonate can have a weight average molecular weight of17,000 to 40,000 g/mol, 17,000 to 35,000 g/mol, 17,000 to 30,000 g/mol,17,000 to 25,000 g/mol, 17,000 to 23,000 g/mol, 17,000 to 22,000 g/mol,18,000 to 22,000, 18,000 to 35,000 g/mol, 18,000 to 30,000 g/mol, 25,000to 30,000 g/mol, 26,000 to 30,000 g/mol, 27,000 to 30,000 g/mol, 28,000to 30,000 g/mol, or 29,000 to 30,000 g/mol. The BPA polycarbonate,optionally having phenol or paracumyl phenol derived endcaps, can have aweight average molecular weight of 17,000 g/mol, 17,500 g/mol, 18,000g/mol, 18,500 g/mol, 19,000 g/mol, 19,500 g/mol, 20,000 g/mol, 20,500g/mol, 21,000 g/mol, 21,500 g/mol, 22,000 g/mol, 22,500 g/mol, 23,000g/mol, 23,500 g/mol, 24,000 g/mol, 24,500 g/mol, 25,000 g/mol, 25,500g/mol, 26,000 g/mol, 26,500 g/mol, 27,000 g/mol, 27,500 g/mol, 28,000g/mol, 28,500 g/mol, 29,000 g/mol, 29,500 g/mol, 30,000 g/mol, 30,500g/mol, 31,000 g/mol, 31,500 g/mol, 32,000 g/mol, 32,500 g/mol, 33,000g/mol, 33,500 g/nmol, 34,000 g/mol, 34,500 g/mol, 35,000 g/mol, 35,500g/mol, 36,000 g/mol, 36,500 g/mol, 37,000 g/mol, 37,500 g/mol, 38,000g/mol, 38,500 g/mol, 39,000 g/mol, 39,500 g/mol, or 40,000 g/mol. TheBPA polycarbonate can have a weight average molecular weight of 18,200g/mol, 18,800 g/mol, 21,800 g/mol, 21,900 g/mol, 29,900 g/mol, or 30,000g/mol. Weight average molecular weight can be determined by GPC usingBPA polycarbonate standards.

The BPA polycarbonates can have a polydispersity index (PDI) of 1.0 to10.0, 2.0 to 7.0, or 2.0 to 3.0. In certain embodiments, the BPApolycarbonates have a PDI of 1.00, 1.50, 2.00, 2.50, 3.00, 3.50, 4.00,4.50, 5.00, 5.50, 6.00, 6.50, 7.00, or 7.50. In certain embodiments, theBPA polycarbonates can have a PDI of 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, 2.8, 2.9, or 3.0. In certain embodiments, the BPA polycarbonateshave a PDI of 2.2 or 2.3.

The BPA polycarbonate can be present in the blend compositions in anamount ranging from 1 to 60 wt %, 3 to 55 wt %, 5 to 50 wt %, or 10 to35 wt %, based on total weight of the composition. The BPA polycarbonatecan be present in the blend compositions in an amount of 1 wt %, 2 wt %,3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt%, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt%, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt%, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt%, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt%, 44 wt %, 45 wt %, 46 wt %, 47 wt %, 48 wt %, 49 wt %, 50 wt %, 51 wt%, 52 wt %, 53 wt %, 54 wt %, 55 wt %, 56 wt %, 57 wt %, 58 wt %, 59 wt%, or 60 wt %, based on total weight of the composition.

In certain embodiments, the blend compositions include a BPApolycarbonate selected from the group consisting of: a PCP end-cappedlinear BPA polycarbonate having a weight average molecular weight of18,200 g/mol [^(±)1,000 g/mol]; a PCP end-capped linear BPApolycarbonate having a weight average molecular weight of 18,800 g/mol[^(±)1,000 g/mol]; a phenol end-capped linear BPA polycarbonate having aweight average molecular weight of 21,800 g/mol [^(±)1,000 g/mol]; a PCPend-capped linear BPA polycarbonate having a weight average molecularweight of 21,900 g/mol [^(±)1,000 g/mol]; a PCP end-capped linear BPApolycarbonate having a weight average molecular weight of 29,900 g/nmol[^(±)1,000 g/mol]; and a phenol end-capped linear BPA polycarbonatehaving a weight average molecular weight of 30,000 g/mol [^(±)1,000g/mol]; or any combination thereof; wherein the weight average molecularweight is as determined by GPC using BPA polycarbonate standards.

The polycarbonate blend compositions can include one or morepolyester-polycarbonate copolymer to enhance one or more of the thermal,mechanical, rheological, and metallization performance of the blendcompositions. Exemplary polyester-polycarbonate copolymer for inclusionin the blend compositions include polycarbonates comprising aliphaticdicarboxylic acid units, and more specifically, polycarbonates includingaliphatic dicarboxylic acids units and units derived from BPA. Thepolyester-polycarbonate copolymers can be prepared by interfacialpolymerization. The polyester-polycarbonate copolymers can be preparedvia a continuous flow reactor (e.g., a tube reactor). Thepolyester-polycarbonate copolymers can have endcaps derived fromparacumyl phenol (PCP), for example.

The polyester-polycarbonate copolymer, such as a poly(aliphaticester)-polycarbonate copolymer, can include 1 to 25 mol % aliphaticdicarboxylic acid content, 0.5 to 10 mol % aliphatic dicarboxylic acidcontent, 1 to 9 mol % aliphatic dicarboxylic acid content, or 3 to 8 mol% aliphatic dicarboxylic acid content. The polyester-polycarbonatecopolymer, such as a poly(aliphatic ester)-polycarbonate copolymer, caninclude 1 mol %, 2 mol %, 3 mol %, 4 mol %, 5 mol %, 6 mol %, 7 mol %, 8mol %, 9 mol %, 10 mol %, 11 mol %, 12 mol %, 13 mol %, 14 mol %, 15 mol%, 16 mol %, 17 mol %, 18 mol %, 19 mol %, 20 mol %, 21 mol %, 22 mol %,23 mol %, 24 mol %, or 25 mol % aliphatic dicarboxylic acid content. Thepolyester-polycarbonate copolymer can include 3 nmol % aliphaticdicarboxylic acid content. The polyester-polycarbonate copolymer caninclude 4 mol % aliphatic dicarboxylic acid content. Thepolyester-polycarbonate copolymer can include 5 mol % aliphaticdicarboxylic acid content. The polyester-polycarbonate copolymer caninclude 6 mol % aliphatic dicarboxylic acid content. Thepolyester-polycarbonate copolymer can include 7 mol % aliphaticdicarboxylic acid content. The polyester-polycarbonate copolymer caninclude 8 mol % aliphatic dicarboxylic acid content.

The poly(aliphatic ester)-polycarbonate copolymer, can include 1 to 25mol % sebacic acid content, 0.5 to 10 mol % sebacic acid content, 1 to 9mol % sebacic acid content, or 3 to 8 mol % sebacic acid content. Thepoly(aliphatic ester)-polycarbonate copolymer, can include 1 mol %, 2mol %, 3 mol %, 4 mol %, 5 mol %, 6 mol %, 7 mol %, 8 nmol %, 9 mol %,10 mol %, 11 mol %, 12 nmol %, 13 mol %, 14 mol %, 15 mol %, 16 mol %,17 mol %, 18 mol %, 19 mol %, 20 mol %, 21 mol %, 22 mol %, 23 mol %, 24mol %, or 25 mol % sebacic acid content. The poly(aliphaticester)-polycarbonate copolymer can include 3 mol % sebacic acid content.The poly(aliphatic ester)-polycarbonate copolymer can include 4 mol %sebacic acid content. The poly(aliphatic ester)-polycarbonate copolymercan include 5 mol % sebacic acid content. The poly(aliphaticester)-polycarbonate copolymer can include 6 mol % sebacic acid content.The poly(aliphatic ester)-polycarbonate copolymer can include 7 mol %sebacic acid content. The poly(aliphatic ester)-polycarbonate copolymercan include 8 mol % sebacic acid content.

The poly(aliphatic ester)-polycarbonate copolymer can have from 4.0 to12.0 mol % of sebacic acid (of the total composition). Thepoly(aliphatic ester)-polycarbonate copolymer can have from 5.0 to 11.0mol %, from 6.0 to 10.0 mol %, from 4.0 to 10.0 mol %, from 7.0 to 9.0mol %, from 7.5 to 8.5 mol %, from 5.0 to 7.0 mol %, or from 5.5 to 6.5mol % of sebacic acid (of the total composition). The poly(aliphaticester)-polycarbonate copolymer can have 8.25 mol % of sebacic acid (ofthe total composition). The poly(aliphatic ester)-polycarbonatecopolymer can have 6.0 mol % of sebacic acid (of the total composition).

The polyester-polycarbonate copolymer, such as a poly(aliphaticester)-polycarbonate copolymer can have a weight average molecularweight of 1,500 to 100,000 g/mol, 1,700 to 50,000 g/mol, 15,000 to45,000 g/mol, 17,000 to 40,000 g/mol, 15,000 to 25,000 g/mol, 15,000 to23,000 g/mol, or 20,000 to 25,000 g/mol. The polyester-polycarbonatecopolymer, such as a poly(aliphatic ester)-polycarbonate copolymer canhave a weight average molecular weight of 15,000 g/mol, 16,000 g/mol,17,000 g/mol, 18,000 g/mol, 19,000 g/mol, 20,000 g/mol, 21,000 g/mol,22,000 g/mol, 23,000 g/mol, 24,000 g/mol, 25,000 g/mol, 26,000 g/mol,27,000 g/mol, 28,000 g/mol, 29,000 g/mol, 30,000 g/mol, 31,000 g/mol,32,000 g/mol, 33,000 g/mol, 34,000 g/mol, 35,000 g/mol, 36,000 g/mol,37,000 g/mol, 38,000 g/mol, 39,000 g/mol, or 40,000 g/mol. Weightaverage molecular weight can be determined by GPC using BPApolycarbonate standards.

The polyester-polycarbonate copolymer, such as a poly(aliphaticester)-polycarbonate copolymer, can be present in the blend compositionsin an amount ranging from 1 to 40 wt %, 5 to 35 wt %, or 10 to 35 wt %,based on total weight of the composition. The polyester-polycarbonatecopolymer, such as a poly(aliphatic ester)-polycarbonate copolymer, canbe present in the blend compositions in an amount of 1 wt %, 2 wt %, 3wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %,12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %,20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %,28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %,36 wt %, 37 wt %, 38 wt %, 39 wt %, or 40 wt %, based on total weight ofthe composition.

The polyester-polycarbonate copolymer, such as a poly(aliphaticester)-polycarbonate copolymer, can have an MVR of 5 to 150 ml/10 min. 7to 125 ml/10 min, 9 to 110 ml/10 min, or 10 to 100 ml/10 min, measuredat 300° C., and a load of 1.2 kilograms according to ASTM D1238-04 orISO 1133.

The polyester-polycarbonate copolymer, such as a poly(aliphaticester)-polycarbonate copolymer, can have an MFR of 20 to 110 g/10 min,45 to 100 g/10, 45 to 60 g/10 min. 85 to 110 g/10 min, or at least 85g/10 min. The polyester-polycarbonate copolymer, such as apoly(aliphatic ester)-polycarbonate copolymer, can have an MFR of 45g/10 min, 50 g/10 min, 55 g/10 min. 60 g/10 min, 65 g/10 min, 70 g/10min, 75 g/10 min, 80 g/10 min, 85 g/10 min, 90 g/10 min. 95 g/10 min,100 g/10 min. 105 g/10 min, 110 g/10 min, 115 g/10 min. or 120 g/10 min,measured according to ASTM D1238.

The polyester-polycarbonate copolymer, such as a poly(aliphaticester)-polycarbonate copolymer, can have a biocontent according toASTM-D-6866 of at least 2 wt %, at least 3 wt %, at least 4 wt %, atleast 5 wt %, at least 6 wt %, at least 7 wt %, at least 8 wt %, atleast 9 wt %, at least 10 wt %, at least 11 wt %, at least 12 wt %, atleast 13 wt %, at least 14 wt %, at least 15 wt %, at least 16 wt %, atleast 17 wt %, at least 18 wt %, at least 19 wt %, at least 20 wt %, atleast 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %, atleast 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, orat least 65 wt % of the composition derived therefrom.

In certain embodiments, the blend compositions include apolyester-polycarbonate copolymer selected from the group consisting of:a PCP end-capped BPA polycarbonate-poly(aliphatic ester) copolymercomprising 6 mol % sebacic acid, and having a weight average molecularweight of 18,000 g/mol [^(±)1,000 g/mol], and a melt flow rate of atleast 85 g/10 min. measured according to ASTM D1238 (300° C., 1.2 kgf);and a PCP end-capped BPA polycarbonate-poly(aliphatic ester) copolymercomprising 6 mole % sebacic acid, and having a weight average molecularweight of 22,000 g/mol [^(±)1,000 g/mol], and a melt flow rate of 45g/10 min to 60 g/10 min, measured according to ASTM D1238 (300° C., 1.2kgf); or a combination thereof; wherein the weight average molecularweight is as determined by GPC using BPA polycarbonate standards.

The polycarbonate blend compositions can include one or more additives.Exemplary additives for inclusion in the blend compositions include, forexample, pentacrythritol tetrastearate (PETS), pentaerythritholtetrakis-(3-dodecylthiopropionate) (SEENOX 412S),tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4′-diylbisphosphonite(PEPQ), monozinc phosphate (MZP), phosphoric acid, hydroxyl octaphenylbenzotriazole, and any combination thereof.

In certain embodiments, the blend compositions include PETS, a phosphitestabilizer (e.g., Iragafos 168), and a hindered phenol (e.g., Irgafos1076). In certain embodiments, the blend compositions include 0.27 wt %PETS, 0.08 wt % phosphite stabilizer (e.g., Iragafos 168), and 0.04 wt %hindered phenol (e.g., Irgafos 1076), based on total weight of thecomposition.

EXAMPLES

Physical testing (e.g., heat deflection temperature, melt volume flowrate, melt flow rate, melt viscosity, melt stability, multiaxial impact)is performed according to ISO or ASTM standards. Unless indicatedotherwise, all test standards refer to those in effect in 2014.

Heat deflection temperature (HDT) is a relative measure of a material'sability to perform for a short time at elevated temperatures whilesupporting a load. The test measures the effect of temperature onstiffness: a standard test specimen is given a defined surface stressand the temperature is raised at a uniform rate. HDT is determined asflatwise under 1.82 MPa or 0.45 MPa loading with 3.2 mm (4 mm for ISO)thickness bar according to ASTM D648-2007 or ISO75-2013. Results arereported in ° C.

Melt volume rate (MVR) is measured at 300° C./2.16 kg or 330° C./2.16 kgas per ASTM D 1238-2010 or ISO1133-2011. Melt viscosity (MV) is measuredaccording to ASTM-D3835-2008 or ISO11443-2005 at a temperature of 300°C. or 316° C. and shear rate of 1500 or 5000 s⁻¹.

Multiaxial impact is measured according to ASTM D3763-2010 or ISO6603-2000. Notched izod impact is measured according to ASTM D256-2010or ISO 180-2000. Tensile modulus is measured according to ASTMD638-2010.

Differential scanning calorimetry (DSC) employing a temperature sweeprate of 20° C./min is used to determine Tgs.

Flammability tests can be performed following the procedure ofUnderwriter's Laboratory Bulletin 94 entitled “rests for Flammability ofPlastic Materials, UL94.” According to this procedure, materials can beclassified as V-0, V-1 or V-2 on the basis of the test results obtainedfor samples of 3.0 millimeter thickness. The samples are made accordingto the UL94 test procedure using standard ASTM molding criteria. Samplesare burned in a vertical orientation after aging for 48 hours at 23° C.,50% relative humidity or 168 hours at 70° C. At least 10 injectionmolded bars are burned for each UL test.

Molecular weight determinations are performed using GPC, using across-linked styrene-divinylbenzene column and calibrated to bisphenol-Apolycarbonate standards using a UV-VIS detector set at 254 nm. Samplesare prepared at a concentration of 1 mg/nil, and eluted at a flow rateof 1.0 ml/min.

Table 1 summarizes the exemplary materials components of thepolycarbonate blend compositions. The listed copolymers andpolycarbonate resins were prepared by methods known in the art. Allother chemical entities were purchased from the commercial sourceslisted.

TABLE 1 PPPBP-PC-1 PPPBP (N-Phenylphenolphthalein- SABIC ylbisphenol,2,2-Bis(4-hydro) - Bisphenol A Copolymer, 32 mol % PPPBP, Mw 23,000g/mol, interfacial polymerization, PCP end- capped, PDI = 2-3 PC-5Linear Bisphenol A polycarbonate produced SABIC by interfacialpolymerization, Mw 21,900 g/mol as determined by GPC using polycarbonatestandards, PCP end-capped, PDI = 2-3 PE-PC-1 Poly(aliphatic ester) -Bisphenol A SABIC polycarbonate copolymer, 6 mole % sebacic acid, Mw18,000 g/mol as determined by GPC using polycarbonate standards, para-cumylphenol (PCP) end-capped, having a melt flow rate of 100 g/10 minmeasured according to ASTM D1238 (300° C., 1.2 kgf). PE-PC-2Poly(aliphatic ester) - Bisphenol A SABIC polycarbonate copolymer, 6mole % sebacic acid, Mw 22,000 g/mol as determined by GPC usingpolycarbonate standards, para- cumylphenol (PCP) end-capped, having amelt flow rate of 55 g/10 min measured according to ASTM D1238 (300° C.,1.2 kgf). PETS Pentaerythritol Tetrastearate LONZA PhosphiteTris(di-t-butylphenyl)phosphite BASF stabilizer Hindered Octadecyl3-(3,5-di-tert-butyl-4- BASF Phenol hydroxyphenyl)propionate BPA4,4′-(propane-2,2-diyl)diphenol SABIC BPADP Bisphenol A diphosphate KSSPotassium diphenylsulfone sulfonate Rimar-K Potassium perfluorobutanesulfonate FYROLFLE oligomeric phosphate ester; Phosphorus ICL IND. X ™Sol-DP Content: 10.7%; Specific Gravity: 1.3; PRODUCTS Melting Range:101-108° C. TSAN Styrene-Acrylonitrile copolymer encapsulated PTFE

General Sebacic Acid Copolyestercarbonate Resin Synthesis Description

Bisphenol-A and sebacic acid are weighed, then transferred to aformulation tank which contains methylene chloride, water, triethyamine(catalyst) and a small amount of aqueous sodium hydroxide. The mixtureis agitated for 5 minutes and then transferred to the polymerizationreactor. Phosgene is added to the reaction mixture over the course of 25minutes. P-cumylphenol is added to the polymerization reactor over thecourse of five minutes during the phosgenation. Aqueous sodium hydroxideis additionally added in order to control reaction pH.

Alternatively, sebacic acid is dissolved in a mixture of water andaqueous sodium hydroxide. Bisphenol-A is weighed, then transferred to aformulation tank which contains methylene chloride, water andtriethylamine (catalyst). The formulation mixture is transferred to thepolymerization reactor. The sebacic acid solution is transferred to thepolymerization reactor. Phosgene is added to the reaction mixture overthe course of 25 minutes. P-cumylphenol is added to the reactor over thecourse of five minutes during the phosgenation. Aqueous sodium hydroxideis additionally added in order to control reaction pH.

After completion of the polymerization, the reaction mixture isdischarged to the centrifuge feed tank. The polymer solution is purifiedby feeding the reaction product to a train of liquid/liquid centrifuges.The first centrifuge stage separates the reaction by product brine fromthe resin solution. The second centrifuge stage removes catalyst fromthe resin solution by washing with dilute aqueous hydrochloric acid. Thethird centrifuge stage removes residual ionic species by washing theresin solution with water.

The purified resin solution is then concentrated by evaporation ofmethylene chloride. The resin is then precipitated by co-feeding theresin solution to a jet with steam to flash off the methylene chloride.Residual methylene chloride is removed from the resin by counter currentcontact with steam. Excess water is removed from the resin using heatedair in a fluidizing dryer.

Procedures as disclosed in U.S. Patent Application Publication No.2013/0196131 can be employed for the synthesis of the poly(aliphaticester)-bisphenol A polycarbonate copolymers described and used herein.

Specific Sebacic Acid Copolyestercarbonate Resin Synthesis ProcessDescription

In a Nalgene plastic container is placed sebacic acid (242 g, 1.19moles), 50% NaOH (280 g, 3.5 moles), and water (2500 mL) (referred to asthe “sebacic acid solution”). The mixture is placed on a platform shakerand mixed until dissolved. To a formulation tank is addeddichloromethane (10 L), deionized water (10 L), bisphenol-A (4268 g,18.71 moles), the sebacic acid solution, para-cumyl phenol (163 g, 0.77moles), triethylamine (50 g, 0.49 moles, 2.5 mol %), and sodiumgluconate (10 g). The mixture is stirred and transferred to a batchreactor. The reactor agitator is started and the circulation flow is setat 80 L/min. Phosgene vapor flow to the reactor is initiated by thedistributed control system (DCS) in three continuous segments separatedby different pH targets. Reaction pH is controlled by DCS addition of50% aqueous NaOH. During segment 1 (50% of total phosgene charge, 1295g, 13.1 moles) the reaction pH target is 7.25. During segment 2(phosgene charge 320 g, 3.2 moles) the reaction pH target is ramped from7.25 to 10.2. Segment 3 (phosgene 965 g, 9.7 moles) maintains a pHtarget of 10.2 until the total phosgene setpoint is reached (2580 g,26.0 moles). A sample of the reactor is obtained and verified to be freeof unreacted BPA and free of chloroformate. Mw of the reaction sample isdetermined by GPC (21,500 g/mol). The reactor is purged with nitrogenand the batch is transferred to centrifuges for HCl/water wash andisolation via steam precipitation, as described above.

PE-PC-1 and PE-PC-2 Manufacture

PE-PC-1 is prepared using reactive chain-chopping chemistry with aredistribution catalyst during extrusion. The poly(aliphaticester)-bisphenol A polycarbonate copolymer prepared in the procedureabove, is mixed one or more additional components (e.g., a mold releaseagent (PETS), a heat stabilizer (Irgaphos)). This mixture is subjectedto reactive chain chopping extrusion with a redistribution catalyst. Themixture is added to a 30 mm co-rotating twin screw (Werner & Pfleiderer;ZSK-30) extruder using a melt temperature of 300° C. with a rate of 20kgs/hr, 20 inches of mercury vacuum and a screw speed of 400 RPM. Aredistribution catalyst (tetrabutyl phosphonium hydroxide, 45% solutionin water) is fed into the extruder using a separate liquid pump feeder.The extrudate is cooled under water and pelletized and dried at 120° C.for 4 hours with a desiccant bed dryer to afford PE-PC-1 (100 g/10minutes melt flow rate at 300° C. under 1.2 kgf).

“PE-PC-2” refers to a high flow ductile thermoplastic resin having a 55g/10 minutes melt flow rate at 300° C. under 1.2 kgf. The PE-PC-2 can bederived from a higher weight average molecular weight poly(aliphaticester)-bisphenol A polycarbonate copolymer than that used to producePE-PC-1. The PE-PC-2 can be prepared in a process analogous to thatdescribed for PE-PC-1 above.

Compositions comprising the thermoplastic composition can bemanufactured by various methods. For example, the poly(aliphaticester)-polycarbonate copolymer, a redistribution catalyst, andadditional components can be first blended in a high speedHENSCHEL-Mixer. Other low shear processes, including but not limited tohand mixing, can also accomplish this blending. The blend can then befed into the throat of a single or twin-screw extruder via a hopper.Alternatively, at least one of the components can be incorporated intothe composition by feeding directly into the extruder at the throat ordownstream through a sidestuffer. Additives can also be compounded intoa masterbatch with a desired polymeric resin and fed into the extruder.The extruder is generally operated at a temperature higher than thatnecessary to cause the composition to flow. The extrudate is immediatelyquenched in a water batch and pelletized. The pellets, so prepared, whencutting the extrudate can be one-fourth inch long or less as desired.Such pellets can be used for subsequent molding, shaping, or forming.

Unless stated otherwise, the phrase “0.4 wt % additives,” “0.39 wt %additives,” or a derivation thereof, as used in the following tables,refers to 0.27 wt % pentaerythritol tetrastearate (PETS)+0.08 wt %phosphite stabilizer (e.g., Iragafos 168)+0.04 wt % hindered phenol(e.g., Irgafos 1076).

Compositions with Polyester-Polycarbonate Copolymers

Polyester-polycarbonate copolymers were incorporated into polycarbonateblend compositions to improve flow, while maintaining good heatperformance, and flame retardance.

Compositions were prepared incorporating a variety of flame retardantagents into the compositions. Table 5 reveals that the addition oftransparent flame retardant materials such as Rimar, KSS, BPADP or SolDPresulted in good flow properties, but a decrease in heat properties.Compositions that included TSAN (3, 6, 9) provided good flame retardantproperties at 3 mm thickness. However, these three compositions losttransparency with the addition of TSAN.

TABLE 5 Composition 1 2 3 4 5 6 7 8 9 PPPBP-PC-1 (%) 65 65 65 65 65 6565 65 65 PC-5 (%) 9.61 9.23 9.03 3.61 4.47 1.37 1.37 PE-PC-1 (%) 25.0 2525 25 25.0 24.8 25 25 24.8 PETS (%) 0.75 0.27 0.27 0.27 0.27 0.27 0.270.27 0.27 Phosphite Stab.; 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08Irgafos 168 (%) Hindered Phenol; 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.040.04 Irgafos 1076 (%) Rimar-K (%) 0.08 0.08 KSS (%) 0.30 0.30 TSAN (%)0.2 0.2 0.2 BPADP (%) 6 9.61 9.61 FyrolflexSolDP (%) 5.14 8.24 8.24 HDT,0.45 MPa, 163 162 161 136 130 129 145 130 130 3.2 mm (° C.) Melt, vis316° C., 130 113 114 83 62 65 83 72 71 5000 s⁻¹ (Pa-s) MFR; 330° C.;2.16 kg, 41 55 57 84 122 126 92 104 108 360 s (g/10 mm) MVR; 330° C.;2.16 kg, 38 52 50 78 110 114 82 96 38 360 s (mL/10 min) MAI TotalEnergy, 63 58 59 62 49 51 61 61 65 23° C. (J) Ductility (%) 80 40 40 5040 40 50 100 80 Tensile Modulus, 2678 2760 2744 3044 3198 3132 2898 30983106 23° C. (Mpa) Elongation at break, 71 72 29 45 22 40 60 47 25 23° C.(%) Flame class - 3 mm V-2 V-2 V-0 none V-2 V-0 V-2 V-2 V-0 Total flametime 176 83 61 x 161 37 240 169 19 (t1 + t2); 23° C., 48 hr (sec) Totalflame time 303 108 45 223 193 9 193 125 7 (t1 + t2); 70° C., 168 hr(sec) Elaine class - 2.5 V-2 — V-2 V-2 — V-2 — — V-0 mm Total flame time210 — 99 190 — 22 — — 55 (t1 + t2); 23° C., 48 hr (sec) Total flame time261 — 94 287 — 5 — — 33 (t1 + t2); 70° C., 168 hr (sec) Flame class -1.5 none V-2 V-2 V-2 V-2 V-2 V-2 V-2 V-2 mm Total flame time 339 147 120135 97 21 138 45 35 (t1 + t2); 23° C., 48 hr (sec) Total flame time —141 232 180 80 52 67 18 71 (t1 + t2); 70° C., 168 hr (sec)

In an attempt to obtain compositions with high modulus properties, glassfibers were incorporated into the compositions (Table 6). Incorporationof glass fibers resulted in increased heat properties (HDT) andincreased modulus, but decreased flow.

TABLE 6 Composition 1 10 11 12 13 14 15 PPPBP-PC-1 (%) 65 58.48 51.9645.42 58.48 51.96 45.42 PC-5 (%) 9.61 8.64 7.67 6.72 8.64 7.67 6.72PE-PC-1 (%) 25.0 22.49 19.98 17.47 22.49 19.98 17.47 PETS (%) 0.75 0.270.27 0.27 0.27 0.27 0.27 Phosphite Stab.; 0.08 0.08 0.08 0.08 0.08 0.080.08 Irgafos 168 (%) Hindered Phenol; 0.04 0.04 0.04 0.04 0.04 0.04 0.04Irgafos 1076 (%) Bonding fiberglass 10 20 30 for Lexan (%) Standard 10micron 10 20 30 PBT glass fiber (%) GPC Mol. Weight (Da) 22883 2253222268 21773 22402 22416 22362 Ash (%) 0 10.4 22.9 31.75 9.84 20.14 33.05HDT, 1.8 MPa (° C.) 150 161 165 165 164 165 165 MVR; 330° C.; 2.16 kg,38 32 31 23 32 28 20 360 s (mL/10 min) MVR; 330° C.; 2.16 kg, 13 11 8 89 7 7 360 s (mL/10 min) Tensile Modulus, 2396 4010 6104 9218 4244 67569270 23° C. (Mpa) Elongation at break, 52.1 6.8 4.4 3.0 6.4 3.3 3.3 23°C. (%) Flex Modulus, 2640 3810 5920 8710 3950 6360 8720 23° C. (Mpa)

Compositions that combined glass fiber and flame retardant agents wereprepared (Table 7). These compositions maintained good heat and flowproperties, while also possessing excellent robust flame retardantproperties, even at 1.0 mm thickness. In addition, these compositionsunexpectedly possessed high impact strength (NII, compositions 17, 21,22, 24, 25).

TABLE 7 Composition 1 16 17 18 19 20 21 22 23 24 25 PPPBP-PC-1 65 6558.48 65.00 65.00 65.00 57.48 50.45 65.00 57.48 50.45 PC-5 (%) 9.61 9.037.76 24.50 1.37 1.37 1.37 PE-PC-1 (%) 25.0 24.70 22.49 24.50 24.30 22.0219.05 24.50 22.02 19.05 PETS (%) 0.75 0.27 0.27 0.27 0.27 0.27 0.27 0.270.27 0.27 0.27 Phosphite Stab; 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.080.08 0.08 0.08 Irgafos 168 (%) Hindered Phenol; 0.04 0.04 0.04 0.04 0.040.04 0.04 0.04 0.04 0.04 0.04 Irgafos 1076 (%) Rimar-K (%) 0.08 0.08 KSS(%) 0.30 0.30 TSAN (%) 0.5 0.5 0.50 0.50 0.70 0.50 0.50 0.50 0.50 0.50BPADP (%) 9.61 9.61 9.61 9.61 9.61 FyrolflexSolDP (%) 8.24 8.24 8.24Standard 10 micron 10 10 20 10 20 PBT glass fiber (%) Tg - DSC (° C.)170 170 171 137 138 136 134 133 138 134 132 HDT, 1.8 Mpa 161 — 168 129128 128 133 130 130 134 132 (° C.) Melt, vis 316° C., 104 81 126 57 6560 70 71 66 76 83 5000 s⁻¹ (Pa-s) MVR; 330° C.; 2.16 kg, 70 177 50 139109 126 86 84 115 76 65 360 s (mL/10 min) Ash (%) 0.03 0.1 10.52 1.181.1 0 11.4 20.97 0.74 10.94 20.78 MAI Total Energy, 51 — 4 4 28 34 5 718 7 7 23° C. (J) NII, 23° C. (J/m) 34 — 40 16 19 14 26 43 19 29 54Tensile Modulus, 2610 — 4126 2996 2956 2968 4556 7020 2888 4620 7066 23°C., 5 mm/min (MPa) Strength at break, 57 — 86 56 55 56 98 123 57 99 12523° C. (MPa) Elongation at break, 23.84 — 6.19 13.96 17.34 25.84 3.612.58 53.65 4.12 2.55 23° C. (%) Tensile Modulus, 2578 — 4114 3000 29682982 4590 6930 2870 4592 7148 23° C., 50 mm/min (MPa) Sterngth at break,57 — 91 70 59 59 99 128 57 105 122 23° C. (MPa) Elongation at break,19.6 — 6.3 9.4 17.4 15.3 3.2 2.5 29.1 4.0 2.2 23° C. (%) Flame class -2.5 V-2 V-1 V-1 V-0 V-0 V-0 V-0 V-0 V-0 V-0 — mm; 23° C., 48 hr V0 2.5mm pFTP; 0 0.15 0.51 1.0 1.0 1.0 1.0 1.0 1.0 1.0 — 23° C., 48 hr V1 2.5mm pFTP; 0 0.94 0.98 1.0 1.0 1.0 1.0 1.0 1.0 1.0 — 23° C., 48 hr Flameclass - 2.5 V2 V0 V1 V0 V0 V0 V0 V0 V0 V0 V0 mm; 70° C., 168 hr V0 2.5mm pFTP; 0.33 0.88 0.83 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 70° C., 368 hrV1 2.5 mm pFTP; 0.41 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 70° C., 168hr Flame class - 1.5 V2 V2 — V2 V2 V2 V0 V0 V1 V0 V0 mm; 23° C., 48 hrV0 1.5 mm pFTP; 0 0 0 0 0 0 1.0 1.0 0.95 1.0 1.0 23° C., 48 hr V1 1.5 mmpFTP; 0 0 0.03 0 0 0 1.0 1.0 1.0 1.0 1.0 23° C., 48 hr Flame class - 1.5V2 V2 V2 V0 V1 V0 V0 V0 V0 V0 V0 mm; 70° C., 168 hr V0 1.5 mm pFTP; 0 00 0.88 0.62 0.87 1.0 1.0 0.95 1.0 1.0 70° C., 168 hr V1 1.5 mm pFTP; 0 00.03 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 70° C., 168 hr Flame class - 1.0 V2None V2 V0 V0 V2 V0 V0 V2 V0 V0 mm; 23° C., 48 hr V0 1.0 mm pFTP; 0 0 01.0 1.0 0.77 1.0 1.0 0.41 1.0 1.0 23° C., 48 hr V1 1.0 mm pFTP: 0 0 01.0 1.0 0.77 1.0 1.0 0.41 1.0 1.0 23° C., 48 hr Flame class - 1.0 V2 V2V2 V2 V2 V2 V0 V0 V0 V0 V0 mm; 70° C., 168 hr V0 1.0 mm pFTP; 0 0 0 0.390.03 0.11 1.0 1.0 0.94 1.0 1.0 70° C., 168 hr V1 1.0 mm pFTP; 0 0 0.20.39 0.03 0.11 1.0 1.0 1.0 1.0 1.0 70° C., 168 hr

While the present invention is described in connection with what ispresently considered to be the most practical and preferred embodiments,it should be appreciated that the invention is not limited to thedisclosed embodiments, and is intended to cover various modificationsand equivalent arrangements included within the spirit and scope of theclaims. Modifications and variations in the present invention can bemade without departing from the novel aspects of the invention asdefined in the claims. The appended claims should be construed broadlyand in a manner consistent with the spirit and the scope of theinvention herein.

For reasons of completeness, various aspects of the present disclosureare set out in the following numbered clauses:

Clause 1. An article comprising a thermoplastic composition comprising:

(a) a first polycarbonate that includes structural units derived from atleast one of:

wherein R^(a) and R^(b) at each occurrence are each independentlyhalogen, C₁-C₁₂ alkyl. C₁-C₁₂ alkenyl. C₃-C₈ cycloalkyl, or C₁-C₁₂alkoxy; p and q at each occurrence are each independently 0 to 4; R¹³ ateach occurrence is independently a halogen or a C₁-C₆ alkyl group; c ateach occurrence is independently 0 to 4; R¹⁴ at each occurrence isindependently a C₁-C₆ alkyl, phenyl, or phenyl substituted with up tofive halogens or C₁-C₆ alkyl groups; R⁸ at each occurrence isindependently C₁-C₁₂ alkyl or halogen, or two R⁸ groups together withthe carbon atoms to which they are attached form a four-, five, orsix-membered cycloalkyl group; and t is 0 to 10; (b) a poly(aliphaticester)-polycarbonate copolymer of the formula:

wherein m is 4 to 18; x+y is 100; and R³ is formula (I) or formula (II)wherein R^(h) is halogen, alkyl, or haloalkyl; n is 0 to 4; and X^(a) isformula (III) or formula (IV) wherein R and R^(d) are each independentlyhydrogen, halogen, alkyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl,heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; andR^(e) is a divalent alkyl group; and (c) optionally a secondpolycarbonate that is a Bisphenol A (BPA) polycarbonate having a weightaverage molecular weight of 17,000 to 40,000 g/mol, as determined by GPCusing BPA polycarbonate standards; wherein the composition has a heatdeflection temperature of at least 120° C., measured at 1.8 MPa inaccordance with ASTM D 648; wherein the composition has a melt viscosityof less than 130 Pa·s, measured in accordance with ISO 11443 at 316° C.at a shear rate of 5000 s⁻¹.

Clause 2. The article of clause 1, further comprising a flame retardant.

Clause 3. The article of clause 1 or 2, further comprising glass fiber.

Clause 4. The article of any of clauses 1-3, further comprising TSAN.

Clause 5. The article of any of clauses 1-4, wherein a molded sample ofthe composition obtained under standard molding conditions has a notchedizod impact energy of at least 20 J/m at 23° C., as measured inaccordance with ASTM D 256.

Clause 6. The article of any one of clauses 1-5, wherein the compositionhas a tensile modulus measured at 5 mm/min of at least 3500 MPa or atleast 4000 MPa, measured in accordance with ASTM D 638.

Clause 7. The article of any one of clauses 1-6, wherein the firstpolycarbonate comprises structural units derived from PPPBP, wherein thePPPBP content is at most 40 mol %, and wherein the first polycarbonatehas a Tg of at least 170° C.

Clause 8. The article of any one of clauses 1-7, wherein the firstpolycarbonate comprises structural units derived from PPPBP, and has aweight average molecular weight of 15,500 to 40,000 g/mol, as determinedby GPC using BPA polycarbonate standards.

Clause 9. The article of any one of clauses 1-8, wherein the firstpolycarbonate is selected from: a para-cumylphenol end-cappedpolycarbonate comprising structural units derived from PPPBP and BPA,having a weight average molecular weight of 20,000 g/mol as determinedby GPC using BPA polycarbonate standards; and a para-cumylphenolend-capped polycarbonate comprising structural units derived from PPPBPand BPA, having a weight average molecular weight of 23,000 g/mol, asdetermined by GPC using BPA polycarbonate standards.

Clause 10. The article of any one of clauses 1-9, wherein thepoly(aliphatic ester)-polycarbonate copolymer has a weight averagemolecular weight of 15,000 to 25,000 g/mol, as determined by GPC usingBPA polycarbonate standards; wherein the poly(aliphaticester)-polycarbonate copolymer has a Tg of at least 100° C.

Clause 11. The article of any one of clauses 1-10, wherein thepoly(aliphatic ester)-polycarbonate copolymer has the formula:

wherein m is 8; and R³ is

Clause 12. The article of any one of clauses 1-11, wherein thepoly(aliphatic ester)-polycarbonate copolymer is selected from apara-cumylphenol end-capped polyester-polycarbonate copolymer comprisingstructural units derived from sebacic acid and BPA, having a weightaverage molecular weight of 18,000 g/mol, as determined by GPC using BPApolycarbonate standards; and a melt flow rate of at least 85 g/10 min,measured according to ASTM D1238 (300° C., 1.2 kgf); and apara-cumylphenol end-capped polyester-polycarbonate copolymer comprisingstructural units derived from sebacic acid and BPA, having a weightaverage molecular weight of 22,000 g/mol, as determined by GPC using BPApolycarbonate standards; and a melt flow rate of 45 g/10 min to 60 g/10min, measured according to ASTM D1238 (300° C., 1.2 kgf).

Clause 13. The article of any one of clauses 1-12, wherein the secondpolycarbonate is a PCP end-capped linear BPA polycarbonate having aweight average molecular weight of 18,200 g/mol, as determined by GPCusing BPA polycarbonate standards; a PCP end-capped linear BPApolycarbonate having a weight average molecular weight of 18,800 g/mol,as determined by GPC using BPA polycarbonate standards; a phenolend-capped linear BPA polycarbonate having a weight average molecularweight of 21,800 g/mol as determined by GPC using BPA polycarbonatestandards; a PCP end-capped linear BPA polycarbonate having a weightaverage molecular weight of 21,900 g/mol as determined by GPC using BPApolycarbonate standards; a PCP end-capped linear BPA polycarbonatehaving a weight average molecular weight of 29,900 g/mol as determinedby GPC using BPA polycarbonate standards; or a phenol end-capped linearBPA polycarbonate having a weight average molecular weight of 30,000g/mol as determined by GPC using BPA polycarbonate standards.

Clause 14. The article of any one of clauses 1-13, wherein the secondpolycarbonate is a BPA polycarbonate produced by interfacial or meltpolymerization, having a weight average molecular weight of 29,900 g/molas determined by GPC using BPA polycarbonate standards.

Clause 15. The article of any one of clauses 2-14, wherein the flameretardant is selected from at least one of potassium perfluorobutanesulfonate, potassium diphenylsulfone sulfonate and an organophosphoruscompound.

Clause 16. The article of clause 15, wherein the organophosphoruscompound is present in an amount effective to provide 0.1 to 1.5% ofphosphorus, based on the weight of the composition.

Clause 17. The article of clause 15, wherein the organophosphoruscompound is present in an amount effective to provide 0.6 to 1.2% ofphosphorus, based on the weight of the composition.

Clause 18. The article of any one of clauses 15-17, wherein theorganophosphorus compound is bisphenol A diphosphate, an oligomericphosphate ester, or a combination thereof.

Clause 19. The article of any one of clauses 1-18, wherein thecomposition comprises 45 to 70 wt % of the first polycarbonate; 15 to 30wt % of the poly(aliphatic ester)-polycarbonate copolymer; optionally 1to 10 wt % of the second polycarbonate; optionally 0.05 to 10 wt % ofthe flame retardant; optionally 5 to 35 wt % of the glass fiber;optionally 0.1 to 2 wt % TSAN; provided that the combined wt % value ofall components does not exceed 100 wt %.

Clause 20. The article according to any one of clauses 1-19, wherein thecomposition is selected from the group consisting of (1) to (7): (1) acomposition comprising 65 wt % of the first polycarbonate; 24.70 wt % ofthe poly(aliphatic ester)-polycarbonate copolymer; 9.03 wt % of thesecond polycarbonate; 0.38 wt % of the flame retardant; 0.50% TSAN and0.39 wt % of additives; (2) a composition comprising 58.48 wt % of thefirst polycarbonate; 22.49 wt % of the poly(aliphaticester)-polycarbonate copolymer; 7.76 wt % of the second polycarbonate;0.38 wt % of the flame retardant; 10.0% of the glass fiber; 0.50% TSANand 0.39 wt % of additives; (3) a composition comprising 65 wt % of thefirst polycarbonate; 24.5 wt % of the poly(aliphaticester)-polycarbonate copolymer; 9.61 wt % of the flame retardant; 0.50%TSAN and 0.39 wt % of additives; (4) a composition comprising 65 wt % ofthe first polycarbonate; 24.3 wt % of the poly(aliphaticester)-polycarbonate copolymer; 9.61 wt % of the flame retardant; 0.70%TSAN and 0.39 wt % of additives; (5) a composition comprising 57.48 wt %of the first polycarbonate; 22.02 wt % of the poly(aliphaticester)-polycarbonate copolymer; 9.61 wt % of the flame retardant; 10% ofthe glass fiber; 0.50% TSAN and 0.39 wt % of additives; (6) acomposition comprising 50.45 wt % of the first polycarbonate; 19.05 wt %of the poly(aliphatic ester)-polycarbonate copolymer; 9.61 wt % of theflame retardant; 20% of the glass fiber; 0.50% TSAN and 0.39 wt % ofadditives; (7) a composition comprising 65 wt % of the firstpolycarbonate; 24.5 wt % of the poly(aliphatic ester)-polycarbonatecopolymer; 1.37% of the second polycarbonate; 8.24 wt % of the flameretardant; 0.50% TSAN and 0.39 wt % of additives; (8) a compositioncomprising 57.48 wt % of the first polycarbonate; 22.02 wt % of thepoly(aliphatic ester)-polycarbonate copolymer; 1.37% of the secondpolycarbonate; 8.24 wt % of the flame retardant; 10% of the glass fiber;0.50% TSAN and 0.39 wt % of additives; (9) a composition comprising50.45 wt % of the first polycarbonate; 19.05 wt % of the poly(aliphaticester)-polycarbonate copolymer; 1.37% of the second polycarbonate; 8.24wt % of the flame retardant; 20% of the glass fiber; 0.50% TSAN and 0.39wt % of additives.

Clause 21. The article of any one of clauses 1-20, wherein a flame barcomprising the composition demonstrates a probability of first time pass(pFTP) of the UL1.94 V0 test of 1.0, tested at a thickness of 2.5 mm.

Clause 22. The article of any one of clauses 1-21, wherein a flame barcomprising the composition demonstrates a probability of first time pass(pFTP) of the UL94 V0 test of 1.0, tested at a thickness of 1.5 mm.

Clause 23. The article of any one of clauses 1-22, wherein a flame barcomprising the composition demonstrates a probability of first time pass(pFTP) of the UL94 V0 test of 1.0, tested at a thickness of 1.0 mm.

Clause 24. The article of any one of clauses 1-23, wherein a flame barcomprising the composition demonstrates a probability of first time pass(pFTP) of the UL94 V0 test of 1.0, tested at a thickness of 0.8 mm.

Clause 25. The article of any one of clauses 1-24, wherein thecomposition comprises 10 wt % to 30 wt % or 10 wt % to 20 wt % glassfiber and a notched izod impact energy of at least 20 J/m, at least 25J/n, at least 30 J/m, at least 35 J/m, at least 40 J/m or at least 45J/m at 23° C., as measured in accordance with ASTM D 256.

Clause 26. The article of any one of clauses 1-25, selected fromelectrical and electronic housings, electrical and electronicconnectors, automotive connectors, light fixtures, light housings,instrument panels, interior trim, center consoles, panels, quarterpanels, rocker panels, trim, fenders, doors, deck lids, trunk lids,hoods, bonnets, roofs, bumpers, fascia, grilles, minor housings, pillarappliqués, cladding, body side moldings, wheel covers, hubcaps, doorhandles, spoilers, window frames, headlamp bezels, tail lamp housings,tail lamp bezels, license plate enclosures, roof racks, circuitbreakers, running boards, helmet or other protective device, firehelmets, and motor vehicle headlight covers, or any combination thereof.

1. An article comprising a thermoplastic composition comprising: (a) afirst polycarbonate that includes structural units derived from at leastone of:

wherein R^(a) and R^(b) at each occurrence are each independentlyhalogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, C₃-C₈ cycloalkyl, or C₁-C₁₂alkoxy; p and q at each occurrence are each independently 0 to 4; R¹³ ateach occurrence is independently a halogen or a C₁-C₆ alkyl group; c ateach occurrence is independently 0 to 4; R¹⁴ at each occurrence isindependently a C₁-C₆ alkyl, phenyl, or phenyl substituted with up tofive halogens or C₁-C₆ alkyl groups; R^(g) at each occurrence isindependently C₁-C₁₂ alkyl or halogen, or two R^(g) groups together withthe carbon atoms to which they are attached form a four-, five, orsix-membered cycloalkyl group; and t is 0 to 10; (b) a poly(aliphaticester)-polycarbonate copolymer of the formula:

wherein m is 4 to 18; x+y is 100; and R³ is formula (I) or formula (II):

wherein R^(h) is halogen, alkyl, or haloalkyl; n is 0 to 4; and X^(a) isformula (III) or formula (IV):

wherein R^(c) and R^(d) are each independently hydrogen, halogen, alkyl,cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and R^(e) is adivalent alkyl group; and (c) optionally a second polycarbonate that isa Bisphenol A polycarbonate having a weight average molecular weight of17,000 to 40,000 g/mol, as determined by gel permeation chromatographyusing Bisphenol A polycarbonate standards; wherein the composition has aheat deflection temperature of at least 120° C., measured at 1.8 MPa inaccordance with ASTM D 648; wherein the composition has a melt viscosityof less than 130 Pa·s, measured in accordance with ISO 11443 at 316° C.at a shear rate of 5000 s⁻¹.
 2. The article of claim 1, furthercomprising a flame retardant.
 3. The article of claim 1, furthercomprising glass fiber.
 4. The article of claim 1, further comprisingTSAN.
 5. The article of claim 1, wherein a molded sample of thecomposition obtained under standard molding conditions has a notchedizod impact energy of at least 20 J/m at 23° C., as measured inaccordance with ASTM D
 256. 6. The article of claim 1, wherein thecomposition has a tensile modulus measured at 5 mm/min of at least 3500MPa or at least 4000 MPa, measured in accordance with ASTM D
 638. 7. Thearticle of claim 1, wherein the first polycarbonate comprises structuralunits derived from 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one,and has a weight average molecular weight of 15,500 to 40,000 g/mol, asdetermined by gel permeation chromatography using Bisphenol Apolycarbonate standards.
 8. The article of claim 1, wherein the firstpolycarbonate is selected from: a para-cumylphenol end-cappedpolycarbonate comprising structural units derived from3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one and Bisphenol A,having a weight average molecular weight of 20,000 g/mol as determinedby gel permeation chromatography using Bisphenol A polycarbonatestandards; and a para-cumylphenol end-capped polycarbonate comprisingstructural units derived from3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one and Bisphenol A,having a weight average molecular weight of 23,000 g/mol, as determinedby gel permeation chromatography using Bisphenol A polycarbonatestandards.
 9. The article of claim 1, wherein the poly(aliphaticester)-polycarbonate copolymer has a weight average molecular weight of15,000 to 25,000 g/mol, as determined by gel permeation chromatographyusing Bisphenol A polycarbonate standards; wherein the poly(aliphaticester)-polycarbonate copolymer has a Tg of at least 100° C.
 10. Thearticle of claim 1, wherein the poly(aliphatic ester)-polycarbonatecopolymer has the formula:

wherein m is 8; and R³ is CH₃


11. The article of claim 1, wherein the poly(aliphaticester)-polycarbonate copolymer is selected from a para-cumylphenolend-capped polyester-polycarbonate copolymer comprising structural unitsderived from sebacic acid and Bisphenol A, having a weight averagemolecular weight of 18,000 g/mol, as determined by gel permeationchromatography using Bisphenol A polycarbonate standards; and a meltflow rate of at least 85 g/10 min, measured according to ASTM D1238 at300° C. and 1.2 kgf); and a para-cumylphenol end-cappedpolyester-polycarbonate copolymer comprising structural units derivedfrom sebacic acid and Bisphenol A, having a weight average molecularweight of 22,000 g/mol, as determined by gel permeation chromatographyusing Bisphenol A polycarbonate standards; and a melt flow rate of 45g/10 min to 60 g/10 min, measured according to ASTM D1238 at 300° C. and1.2 kgf).
 12. The article of claim 1, wherein the second polycarbonateis a para-cumylphenol end-capped linear Bisphenol A polycarbonate havinga weight average molecular weight of 18,200 g/mol, as determined by gelpermeation chromatography using Bisphenol A polycarbonate standards; apara-cumylphenol end-capped linear Bisphenol A polycarbonate having aweight average molecular weight of 18,800 g/mol, as determined by gelpermeation chromatography using Bisphenol A polycarbonate standards; aphenol end-capped linear Bisphenol A polycarbonate having a weightaverage molecular weight of 21,800 g/mol as determined by gel permeationchromatography using Bisphenol A 6 of 10 polycarbonate standards; apara-cumylphenol end-capped linear Bisphenol A polycarbonate having aweight average molecular weight of 21,900 g/mol as determined by gelpermeation chromatography using Bisphenol A polycarbonate standards; apara-cumylphenol end-capped linear Bisphenol A polycarbonate having aweight average molecular weight of 29,900 g/mol as determined by gelpermeation chromatography using Bisphenol A polycarbonate standards; ora phenol end-capped linear Bisphenol A polycarbonate having a weightaverage molecular weight of 30,000 g/mol as determined by gel permeationchromatography using Bisphenol A polycarbonate standards.
 13. Thearticle of claim 1, wherein the second polycarbonate is a Bisphenol Apolycarbonate produced by interfacial or melt polymerization, having aweight average molecular weight of 29,900 g/mol as determined by gelpermeation chromatography using Bisphenol A polycarbonate standards. 14.The article of claim 1, wherein the flame retardant is selected from atleast one of potassium perfluorobutane sulfonate, potassiumdiphenylsulfone sulfonate and an organophosphorus compound.
 15. Thearticle of claim 14, wherein the organophosphorus compound is present inan amount effective to provide 0.1% to 1.5% of phosphorus, based on theweight of the composition.
 16. The article of claim 14, wherein theorganophosphorus compound is bisphenol A diphosphate, an oligomericphosphate ester, or a combination thereof.
 17. The article of claim 1,wherein the composition comprises 45 to 70 wt % of the firstpolycarbonate; 15 to 30 wt % of the poly(aliphatic ester)-polycarbonatecopolymer; optionally 1 to 10 wt % of the second polycarbonate;optionally 0.05 to 10 wt % of the flame retardant; optionally 5 to 35 wt% of the glass fiber; optionally 0.1 to 2 wt % TSAN; provided that thecombined wt % value of all components does not exceed 100 wt %.
 18. Thearticle according to claim 1, wherein the composition is selected fromthe group consisting of (1) to (9): (1) a composition comprising 65 wt %of the first polycarbonate; 24.70 wt % of the poly(aliphaticester)-polycarbonate copolymer; 9.03 wt % of the second polycarbonate;0.38 wt % of the flame retardant; 0.50% TSAN and 0.39 wt % of additives;(2) a composition comprising 58.48 wt % of the first polycarbonate;22.49 wt % of the poly(aliphatic ester)-polycarbonate copolymer; 7.76 wt% of the second polycarbonate; 0.38 wt % of the flame retardant; 10.0%of the glass fiber; 0.50% TSAN and 0.39 wt % of additives; (3) acomposition comprising 65 wt % of the first polycarbonate; 24.5 wt % ofthe poly(aliphatic ester)-polycarbonate copolymer; 9.61 wt % of theflame retardant; 0.50% TSAN and 0.39 wt % of additives; (4) acomposition comprising 65 wt % of the first polycarbonate; 24.3 wt % ofthe poly(aliphatic ester)-polycarbonate copolymer; 9.61 wt % of theflame retardant; 0.70% TSAN and 0.39 wt % of additives; (5) acomposition comprising 57.48 wt % of the first polycarbonate; 22.02 wt %of the poly(aliphatic ester)-polycarbonate copolymer; 9.61 wt % of theflame retardant; 10% of the glass fiber; 0.50% TSAN and 0.39 wt % ofadditives; (6) a composition comprising 50.45 wt % of the firstpolycarbonate; 19.05 wt % of the poly(aliphatic ester)-polycarbonatecopolymer; 9.61 wt % of the flame retardant; 20% of the glass fiber;0.50% TSAN and 0.39 wt % of additives; (7) a composition comprising 65wt % of the first polycarbonate; 24.5 wt % of the poly(aliphaticester)-polycarbonate copolymer; 1.37% of the second polycarbonate; 8.24wt % of the flame retardant; 0.50% TSAN and 0.39 wt % of additives; (8)a composition comprising 57.48 wt % of the first polycarbonate; 22.02 wt% of the poly(aliphatic ester)-polycarbonate copolymer; 1.37% of thesecond polycarbonate; 8.24 wt % of the flame retardant; 10% of the glassfiber; 0.50% TSAN and 0.39 wt % of additives; (9) a compositioncomprising 50.45 wt % of the first polycarbonate; 19.05 wt % of thepoly(aliphatic ester)-polycarbonate copolymer; 1.37% of the secondpolycarbonate; 8.24 wt % of the flame retardant; 20% of the glass fiber;0.50% TSAN and 0.39 wt % of additives.
 19. The article of claim 1,wherein a flame bar comprising the composition demonstrates aprobability of first time pass (pFTP) of the UL94 V0 test of 1.0, testedat a thickness of 2.5 mm, 1.5 mm, 1.0 mm or 0.8 mm at 23° C. for 48hours or 70° C. for 168 hours.
 20. The article of claim 1, selected fromelectrical and electronic housings, electrical and electronicconnectors, automotive connectors, light fixtures, light housings,instrument panels, interior trim, center consoles, panels, quarterpanels, rocker panels, trim, fenders, doors, deck lids, trunk lids,hoods, bonnets, roofs, bumpers, fascia, grilles, minor housings, pillarappliqués, cladding, body side moldings, wheel covers, hubcaps, doorhandles, spoilers, window frames, headlamp bezels, tail lamp housings,tail lamp bezels, license plate enclosures, roof racks, circuitbreakers, running boards, helmet or other protective device, firehelmets, and motor vehicle headlight covers, or any combination thereof.